JP5690634B2 - Hydrorefining catalyst and method for producing hydrocarbon oil - Google Patents

Hydrorefining catalyst and method for producing hydrocarbon oil Download PDF

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JP5690634B2
JP5690634B2 JP2011080572A JP2011080572A JP5690634B2 JP 5690634 B2 JP5690634 B2 JP 5690634B2 JP 2011080572 A JP2011080572 A JP 2011080572A JP 2011080572 A JP2011080572 A JP 2011080572A JP 5690634 B2 JP5690634 B2 JP 5690634B2
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catalyst
fraction
hydrorefining
oil
mass
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JP2012214604A (en
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祐一 田中
祐一 田中
拓弥 新妻
拓弥 新妻
和彦 田坂
和彦 田坂
真理絵 岩間
真理絵 岩間
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Cosmo Oil Co Ltd
Japan Petroleum Exploration Co Ltd
Inpex Corp
Japan Oil Gas and Metals National Corp
Nippon Steel Engineering Co Ltd
Eneos Corp
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Cosmo Oil Co Ltd
Japan Petroleum Exploration Co Ltd
Inpex Corp
Japan Oil Gas and Metals National Corp
JXTG Nippon Oil and Energy Corp
Nippon Steel Engineering Co Ltd
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Application filed by Cosmo Oil Co Ltd, Japan Petroleum Exploration Co Ltd, Inpex Corp, Japan Oil Gas and Metals National Corp, JXTG Nippon Oil and Energy Corp, Nippon Steel Engineering Co Ltd filed Critical Cosmo Oil Co Ltd
Priority to CA2831737A priority patent/CA2831737C/en
Priority to CN2012800154916A priority patent/CN103459015A/en
Priority to MYPI2013003529A priority patent/MY162457A/en
Priority to AP2013007191A priority patent/AP3496A/en
Priority to AU2012233954A priority patent/AU2012233954B2/en
Priority to EA201391410A priority patent/EA028397B1/en
Priority to CN201710220135.2A priority patent/CN107051427A/en
Priority to BR112013025296-0A priority patent/BR112013025296B1/en
Priority to PCT/JP2012/057764 priority patent/WO2012133316A1/en
Priority to US14/008,246 priority patent/US9475036B2/en
Priority to EP12764926.7A priority patent/EP2692429A4/en
Publication of JP2012214604A publication Critical patent/JP2012214604A/en
Priority to ZA2013/07561A priority patent/ZA201307561B/en
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Description

本発明は、水素化精製触媒及びその水素化精製触媒を用いる炭化水素油の製造方法に関する。   The present invention relates to a hydrorefining catalyst and a method for producing a hydrocarbon oil using the hydrorefining catalyst.

近年、環境に対する意識の高まりから、硫黄分及び芳香族炭化水素等の環境負荷物質の含有量が低い液体燃料が求められている。このような観点から、硫黄分及び芳香族炭化水素を実質的に含まず、脂肪族炭化水素に富む燃料油基材、特に灯油・軽油基材を製造できる技術として、天然ガス等の炭化水素原料から改質反応により合成ガス（一酸化炭素ガスと水素ガスとを主成分とする混合ガス）を製造し、この合成ガスからフィッシャー・トロプシュ合成反応（以下、「ＦＴ合成反応」ということもある。）により炭化水素を合成し、更にこの炭化水素を水素化処理及び分留により精製することにより燃料油基材を得る技術が注目されている（例えば特許文献１を参照。）。この技術はＧＴＬ（Gas To Liquids）プロセスと呼ばれる。   In recent years, liquid fuels having a low content of environmentally hazardous substances such as sulfur and aromatic hydrocarbons have been demanded due to an increase in environmental awareness. From this point of view, as a technology capable of producing a fuel oil base material that is substantially free of sulfur and aromatic hydrocarbons and rich in aliphatic hydrocarbons, particularly kerosene / light oil base materials, hydrocarbon raw materials such as natural gas A synthesis gas (mixed gas containing carbon monoxide gas and hydrogen gas as main components) is produced from the synthesis gas, and the Fischer-Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”) may be used. ), And a technique for obtaining a fuel oil base material by refining the hydrocarbon by hydrotreating and fractional distillation has attracted attention (see, for example, Patent Document 1). This technique is called a GTL (Gas To Liquids) process.

合成ガスからＦＴ合成反応によって得られる合成油（以下、「ＦＴ合成油」ということもある。）は、幅広い炭素数分布を有する脂肪族炭化水素類を主成分とする混合物である。このＦＴ合成油を沸点に応じて分留することにより、ナフサ留分、中間留分及びワックス留分を得ることができる。そして、これら各留分のうち中間留分は、灯油・軽油基材に相当する最も有用な留分であり、これを高い収率で得ることが望まれる。   A synthetic oil obtained from a synthesis gas by an FT synthesis reaction (hereinafter sometimes referred to as “FT synthetic oil”) is a mixture containing aliphatic hydrocarbons having a wide carbon number distribution as a main component. By fractionating this FT synthetic oil according to the boiling point, a naphtha fraction, a middle fraction, and a wax fraction can be obtained. Of these fractions, the middle fraction is the most useful fraction corresponding to the kerosene / light oil base, and it is desired to obtain this in a high yield.

一方、ＦＴ合成反応においては、主生成物である飽和脂肪族炭化水素の他に、副生成物として、オレフィン類並びに一酸化炭素由来の酸素原子を含むアルコール類等の含酸素化合物が生成し、これらの副生成物（不純物）は、ＦＴ合成油を分留して得られるナフサ留分や中間留分に多く含まれる。そして、これらの不純物を含む炭化水素を燃料として使用した場合、エンジンの構成材料が損傷を受けるおそれがあるため、これらの不純物を除去する必要がある。この不純物の除去は、ＧＴＬプロセスにおいてＦＴ合成油を精製するアップグレーディング工程において、不純物を含むナフサ留分、中間留分等の炭化水素油を水素化精製することにより行なうことができる。   On the other hand, in the FT synthesis reaction, in addition to saturated aliphatic hydrocarbons as main products, oxygen-containing compounds such as olefins and alcohols containing carbon monoxide-derived oxygen atoms are produced as by-products, These by-products (impurities) are abundant in naphtha fractions and middle fractions obtained by fractionating FT synthetic oil. And when the hydrocarbon containing these impurities is used as a fuel, since a constituent material of an engine may be damaged, it is necessary to remove these impurities. This removal of impurities can be performed by hydrorefining hydrocarbon oils such as naphtha fraction and middle distillate containing impurities in the upgrading step of refining FT synthetic oil in the GTL process.

また、ＦＴ合成反応によって生成する炭化水素は基本的に直鎖状脂肪族炭化水素であり、直鎖状脂肪族炭化水素は結晶性が高いことから、これを多く含む燃料油は低温において流動性を失う。そのため、灯油・軽油基材となる中間留分においては、水素化異性化により、直鎖状脂肪族炭化水素を分枝鎖状炭化水素に転化し、低温流動性の改良を行なうことが必要となる。この水素化異性化は、前記の水素化精製と同時に行なわれることが一般的である。   In addition, hydrocarbons produced by the FT synthesis reaction are basically linear aliphatic hydrocarbons, and since linear aliphatic hydrocarbons have high crystallinity, fuel oils containing a large amount of these are fluid at low temperatures. Lose. For this reason, it is necessary to improve low-temperature fluidity by converting straight-chain aliphatic hydrocarbons into branched-chain hydrocarbons by hydroisomerization in the middle distillate serving as a kerosene / light oil base. Become. This hydroisomerization is generally performed simultaneously with the above hydrorefining.

中間留分の水素化異性化を伴う水素化精製を行なう水素化精製工程には、ゼオライト及び／又は非晶性複合金属酸化物等の固体酸性を有する担体に、周期表第８族〜第１０族の貴金属から選択される水素化能を有する活性金属が担持された水素化精製触媒が用いられる（例えば特許文献２、３を参照。）。   In the hydrorefining step for hydrorefining with hydroisomerization of the middle distillate, a group having a solid acidity such as zeolite and / or amorphous composite metal oxide is added to periodic table groups 8 to 10. A hydrorefining catalyst on which an active metal having a hydrogenation ability selected from group Noble metals is supported is used (see, for example, Patent Documents 2 and 3).

上記中間留分の水素化精製工程において使用する水素化精製触媒は、前述の水素化精製及び水素化異性化に対する活性の他に、不可避的に分解反応（水素化分解反応）、すなわち炭化水素の炭素−炭素結合を開裂して分子量を低下させる反応に対する活性も有する。そのため、中間留分を水素化精製工程に供すると、中間留分の沸点範囲よりも低い沸点を有する軽質留分が一部生成する。この軽質留分の生成は、中間留分の収率の低下に繋がるため、抑制することが好ましい。   The hydrorefining catalyst used in the above-mentioned middle distillate hydrorefining process inevitably has a decomposition reaction (hydrocracking reaction), that is, a hydrocarbon reaction, in addition to the above-mentioned activities for hydrorefining and hydroisomerization. It also has activity for reactions that cleave carbon-carbon bonds and reduce molecular weight. For this reason, when the middle distillate is subjected to a hydrorefining step, a light fraction having a boiling point lower than the boiling range of the middle distillate is partially generated. Since the production | generation of this light fraction leads to the fall of the yield of a middle fraction, it is preferable to suppress.

特開２００４−３２３６２６号公報JP 2004-323626 A 特開２００８−１６９３５５号公報JP 2008-169355 A 特開２００７−２６９９０１号公報JP 2007-269901 A

しかし、水素化精製触媒において、担体のもつ固体酸性を弱める等の方法により分解反応に対する活性を抑制すると、同時に水素化異性化活性も低下し、中間留分の収率は向上するものの、得られる中間留分の燃料油としての低温流動性は十分に向上しないとの問題があった。水素化精製触媒の水素化異性化活性を高めて分解活性を抑制する方法については未だ十分な検討がなされていない。   However, in the hydrorefining catalyst, if the activity against the decomposition reaction is suppressed by a method such as weakening the solid acidity of the support, the hydroisomerization activity is also reduced and the yield of the middle distillate is improved, but it is obtained. There was a problem that the low temperature fluidity as a middle distillate fuel oil was not sufficiently improved. A method for suppressing the decomposition activity by increasing the hydroisomerization activity of the hydrorefining catalyst has not yet been sufficiently studied.

本発明は、上記事情に鑑みてなされたものであり、高い水素化異性化活性と抑制された分解活性を有し、低温流動性に優れた中間留分を高い収率で得ることができる水素化精製触媒、及び該水素化精製触媒を用いる炭化水素油の製造方法を提供することを目的とする。   The present invention has been made in view of the above circumstances, has a high hydroisomerization activity and a suppressed decomposition activity, and can obtain a middle distillate excellent in low-temperature fluidity in a high yield. An object of the present invention is to provide a hydrorefining catalyst and a method for producing a hydrocarbon oil using the hydrotreating catalyst.

上記課題を解決するために本発明者らは鋭意検討を行った結果、有機化合物由来の炭素質物質を特定の量含有する特定の水素化精製触媒が、直鎖状脂肪族炭化水素に対する水素化異性化活性は十分有しつつ分解活性は抑制されており、低温流動性に優れた中間留分、中でも軽油留分の収率を高めることができることを見出し、この知見に基づいて本発明を完成するに至った。   In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and as a result, a specific hydrorefining catalyst containing a specific amount of a carbonaceous material derived from an organic compound is capable of hydrogenating linear aliphatic hydrocarbons. It has been found that it has sufficient isomerization activity and cracking activity is suppressed, and can improve the yield of middle distillate with excellent low-temperature fluidity, especially light oil distillate. Based on this finding, the present invention has been completed. It came to do.

すなわち本発明は、固体酸性を有する非晶性複合金属酸化物を含む担体と、前記担体に担持された周期表第８族〜第１０族の貴金属から選択される少なくとも一種の活性金属と、を含有してなる水素化精製触媒であって、水素化精製触媒は炭素原子を含む炭素質物質を含有し、水素化精製触媒における炭素質物質の含有量が炭素原子換算で０．０５〜１質量％である水素化精製触媒を提供する。   That is, the present invention comprises a support containing an amorphous composite metal oxide having solid acidity, and at least one active metal selected from Group 8 to Group 10 noble metals supported on the support. A hydrotreating catalyst comprising a hydrotreating catalyst containing a carbonaceous material containing carbon atoms, wherein the content of the carbonaceous material in the hydrotreating catalyst is 0.05 to 1 mass in terms of carbon atoms. % Hydrotreating catalyst is provided.

上記構成を有する本発明の水素化精製触媒によれば、直鎖状脂肪族炭化水素に富む中間留分が含まれる原料油を水素化精製して、分枝鎖状脂肪族炭化水素に富み、低温流動性に優れる中間留分を高い収率で得ることができる。   According to the hydrorefining catalyst of the present invention having the above-described configuration, the raw oil containing a middle distillate rich in linear aliphatic hydrocarbons is hydrorefined to be rich in branched aliphatic hydrocarbons, A middle distillate having excellent low-temperature fluidity can be obtained in a high yield.

本発明の水素化精製触媒においては、非晶性複合金属酸化物がシリカジルコニア、シリカアルミナ及びアルミナボリアから選択される少なくとも一種であることが好ましい。この水素化精製触媒を直鎖状脂肪族炭化水素に富む中間留分を含む原料油の水素化精製に用いた場合、分枝鎖状脂肪族炭化水素に富み、低温流動性に優れる中間留分を一層高い収率で得ることができる。   In the hydrorefining catalyst of the present invention, the amorphous composite metal oxide is preferably at least one selected from silica zirconia, silica alumina, and alumina boria. When this hydrorefining catalyst is used for hydrorefining feedstock containing middle distillates rich in linear aliphatic hydrocarbons, middle distillates rich in branched aliphatic hydrocarbons and excellent in low-temperature fluidity Can be obtained in a higher yield.

また、本発明の水素化精製触媒においては、貴金属が白金であることが好ましい。この水素化精製触媒を用いた場合、分枝鎖状脂肪族炭化水素に富み、低温流動性に一層優れる中間留分を得ることができる。   In the hydrorefining catalyst of the present invention, the noble metal is preferably platinum. When this hydrorefining catalyst is used, it is possible to obtain a middle distillate rich in branched chain aliphatic hydrocarbons and further excellent in low-temperature fluidity.

本発明はまた、分子状水素の共存下、沸点が２５〜３６０℃の範囲にある直鎖状脂肪族炭化水素を８０質量％以上含み且つ沸点が１５０〜３６０℃の範囲にある直鎖状脂肪族炭化水素を２０質量％以上含む原料油を、上記本発明の水素化精製触媒に接触させる炭化水素油の製造方法を提供する。   The present invention also provides a linear fat containing 80% by mass or more of a linear aliphatic hydrocarbon having a boiling point in the range of 25 to 360 ° C. and having a boiling point of 150 to 360 ° C. in the presence of molecular hydrogen. Provided is a method for producing a hydrocarbon oil in which a feedstock containing 20% by mass or more of a group hydrocarbon is brought into contact with the hydrorefining catalyst of the present invention.

本発明の炭化水素油の製造方法によれば、本発明の水素化精製触媒を用いることにより、上記原料油から、分枝鎖状脂肪族炭化水素に富み、低温流動性に優れる中間留分を高い収率で得ることができる。   According to the method for producing a hydrocarbon oil of the present invention, by using the hydrorefining catalyst of the present invention, a middle distillate rich in branched aliphatic hydrocarbons and excellent in low-temperature fluidity can be obtained from the above raw material oil. High yield can be obtained.

本発明の炭化水素油の製造方法においては、上記原料油がフィッシャー・トロプシュ合成反応により得られる合成油であることが好ましい。原料油としてフィッシャー・トロプシュ合成反応により得られる合成油を用いることにより、硫黄分及び芳香族炭化水素を含まず、分枝鎖状脂肪族炭化水素に富み、低温流動性に優れる中間留分を高い収率で得ることができる。   In the method for producing a hydrocarbon oil of the present invention, the raw material oil is preferably a synthetic oil obtained by a Fischer-Tropsch synthesis reaction. By using synthetic oil obtained by Fischer-Tropsch synthesis reaction as raw material oil, it contains no sulfur and aromatic hydrocarbons, is rich in branched chain aliphatic hydrocarbons, and has high middle distillate with excellent low-temperature fluidity The yield can be obtained.

本発明によれば、高い水素化異性化活性と抑制された分解活性を有し、低温流動性に優れた中間留分を高い収率で得ることができる水素化精製触媒、及び該水素化精製触媒を用いる炭化水素油の製造方法を提供することできる。これにより、直鎖状脂肪族炭化水素に富む原料油から、分枝鎖状脂肪族炭化水素に富み、低温流動性に優れる中間留分を高い収率で得ることができる。   According to the present invention, a hydrorefining catalyst having high hydroisomerization activity and suppressed cracking activity and capable of obtaining a middle distillate excellent in low-temperature fluidity in high yield, and the hydrorefining A method for producing a hydrocarbon oil using a catalyst can be provided. Thereby, a middle distillate rich in branched aliphatic hydrocarbons and excellent in low-temperature fluidity can be obtained in high yield from a raw material oil rich in linear aliphatic hydrocarbons.

本発明の炭化水素油の製造方法の一実施形態が実施される炭化水素油の製造装置を示す概略構成図である。It is a schematic block diagram which shows the manufacturing apparatus of the hydrocarbon oil by which one Embodiment of the manufacturing method of the hydrocarbon oil of this invention is implemented.

まず、本発明の水素化精製触媒の好ましい実施形態について説明する。本実施形態の水素化精製触媒は、固体酸性を有する非晶性複合金属酸化物を含む担体と、前記担体に担持された周期表第８族〜第１０族の貴金属から選択される少なくとも一種の活性金属と、を含有してなる水素化精製触媒であって、水素化精製触媒は炭素原子を含む炭素質物質を含有し、水素化精製触媒における炭素質物質の含有量が炭素原子換算で０．０５〜１質量％であることを特徴とする。なお、水素化精製触媒における炭素質物質の上記含有量は、触媒の全質量を基準とした値である。   First, a preferred embodiment of the hydrorefining catalyst of the present invention will be described. The hydrorefining catalyst of this embodiment is at least one selected from a carrier containing an amorphous composite metal oxide having solid acidity and a noble metal of Group 8 to Group 10 supported on the carrier. And a hydrorefining catalyst comprising a carbonaceous material containing carbon atoms, and the content of the carbonaceous material in the hydrotreating catalyst is 0 in terms of carbon atoms. 0.05 to 1% by mass. The content of the carbonaceous material in the hydrotreating catalyst is a value based on the total mass of the catalyst.

本実施形態の水素化精製触媒を構成する担体に含まれる固体酸性を有する非晶性複合金属酸化物としては、例えば、アルミナ、シリカ、チタニア、ジルコニア、ボリア、マグネシア等の金属酸化物単位から選択される２種又は３種以上の組み合わせからなる複合金属酸化物が挙げられる。   As the amorphous complex metal oxide having solid acidity contained in the support constituting the hydrorefining catalyst of the present embodiment, for example, selected from metal oxide units such as alumina, silica, titania, zirconia, boria and magnesia. The composite metal oxide which consists of 2 types, or 3 types or more of a combination made.

固体酸性を有する非晶性複合金属酸化物の具体的な例としては、シリカアルミナ、シリカジルコニア、アルミナボリア、アルミナジルコニア、シリカチタニア、シリカマグネシア等が挙げられる。これらの中でも、シリカアルミナ、シリカジルコニア、アルミナボリアが好ましく、シリカジルコニアがより好ましい。   Specific examples of the amorphous composite metal oxide having solid acidity include silica alumina, silica zirconia, alumina boria, alumina zirconia, silica titania, silica magnesia and the like. Among these, silica alumina, silica zirconia, and alumina boria are preferable, and silica zirconia is more preferable.

前記担体は、少量のゼオライトを含んでもよい。この場合に好ましいゼオライトとしては、超安定Ｙ（ＵＳＹ）型ゼオライト、Ｙ型ゼオライト、モルデナイト及びベータゼオライトなどが挙げられる。この場合の、ゼオライトの含有量は特に限定されないが、担体の全質量を基準として０．５〜１０質量％が好ましく、１〜５質量％がより好ましい。   The carrier may contain a small amount of zeolite. Preferred zeolites in this case include ultrastable Y (USY) type zeolite, Y type zeolite, mordenite, and beta zeolite. The zeolite content in this case is not particularly limited, but is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass based on the total mass of the carrier.

前記担体は、担体の成型性及び機械的強度の向上を目的として、バインダが配合されていてもよい。好ましいバインダとしては、アルミナ、シリカ、マグネシア等が挙げられる。担体にバインダを配合する場合のその配合量は特に限定されないが、担体の全質量を基準として２０〜９８質量％、好ましくは３０〜９６質量％である。   The carrier may contain a binder for the purpose of improving the moldability and mechanical strength of the carrier. Preferred binders include alumina, silica, magnesia and the like. The blending amount of the binder when blended with the carrier is not particularly limited, but is 20 to 98% by mass, preferably 30 to 96% by mass based on the total mass of the carrier.

前記担体は、成型されたものが好ましい。成型された担体の形状は特に限定されないが、球状、円筒状、三つ葉型・四つ葉型の断面を有する異形円筒状、ディスク状等が挙げられる。担体の成型方法は限定されず、押出成型、打錠成型等の公知の方法が用いられる。成型された担体は通常焼成される。   The carrier is preferably a molded one. The shape of the molded carrier is not particularly limited, and examples thereof include a spherical shape, a cylindrical shape, a modified cylindrical shape having a three-leaf type / four-leaf type cross section, and a disk shape. The method for molding the carrier is not limited, and known methods such as extrusion molding and tableting molding are used. The molded carrier is usually fired.

本実施形態の水素化精製触媒において担体に担持される活性金属としては、周期表第８族〜第１０族の貴金属から選択される少なくとも一種である。活性金属の具体的な例としては、第８族の貴金属としてはルテニウム及びオスミウム、第９族の貴金属としてはロジウム及びイリジウム、第１０族の貴金属としてはパラジウム及び白金である。これらの中でも、白金、パラジウムが好ましく、白金がより好ましい。また、白金−パラジウムの組み合わせも好ましく用いられる。なお、ここで周期表とは、ＩＵＰＡＣ（International Union of Pure and Applied Chemistry（国際純正・応用化学連合））の規定に基づく長周期型の元素の周期表をいう。   The active metal supported on the carrier in the hydrorefining catalyst of the present embodiment is at least one selected from noble metals of Groups 8 to 10 of the periodic table. Specific examples of the active metal include ruthenium and osmium as the group 8 noble metal, rhodium and iridium as the group 9 noble metal, and palladium and platinum as the group 10 noble metal. Among these, platinum and palladium are preferable, and platinum is more preferable. A combination of platinum and palladium is also preferably used. Here, the periodic table refers to a periodic table of long-period elements based on the provisions of IUPAC (International Union of Pure and Applied Chemistry).

本実施形態の水素化精製触媒において担体に担持される活性金属の含有量としては、担体の質量を基準として、金属原子換算で０．１〜３質量％であることが好ましい。活性金属の含有量が前記下限値未満の場合には、水素化精製及び水素化異性化が充分に進行しない傾向にある。一方、活性金属の含有量が前記上限値を超える場合には、活性金属の分散が低下して触媒の活性が低下する傾向があり、また触媒コストが上昇する。   The content of the active metal supported on the support in the hydrorefining catalyst of the present embodiment is preferably 0.1 to 3% by mass in terms of metal atoms based on the mass of the support. When the content of the active metal is less than the lower limit, hydrorefining and hydroisomerization tend not to proceed sufficiently. On the other hand, when the content of the active metal exceeds the above upper limit, the dispersion of the active metal tends to decrease, and the activity of the catalyst tends to decrease, and the catalyst cost increases.

本実施形態の水素化精製触媒は、有機化合物由来の炭素原子を含む炭素質物質を、水素化精製触媒における炭素質物質の含有量が炭素原子換算で０．０５〜１質量％となる割合で含有する。この有機化合物由来の炭素質物質としては、例えば、有機化合物を加熱して炭化させることにより得られる炭化物が挙げられる。この炭化物には、炭素原子あるいは炭素原子と少量の水素原子及び／又は酸素原子等から構成され、明確に構造が特定されない炭素状の物質も包含される。本発明に係る炭素質物質は、例えば、本発明に係る水素化精製触媒を構成する担体又は後述する水素化精製触媒の前駆体に有機化合物を添加し、これを焼成又は加熱することにより、当該水素化精製触媒中に生成させることができる。   The hydrorefining catalyst of this embodiment is a ratio in which the content of the carbonaceous material in the hydrotreating catalyst is 0.05 to 1% by mass in terms of carbon atoms. contains. Examples of the carbonaceous material derived from the organic compound include a carbide obtained by heating and carbonizing the organic compound. This carbide includes a carbon-like substance which is composed of carbon atoms or carbon atoms and a small amount of hydrogen atoms and / or oxygen atoms and whose structure is not clearly specified. The carbonaceous material according to the present invention is obtained by, for example, adding an organic compound to a carrier constituting the hydrorefining catalyst according to the present invention or a precursor of a hydrorefining catalyst described later, and firing or heating the compound. It can be produced in a hydrorefining catalyst.

炭素質物質の触媒中の含有量が０．０５質量％未満である場合には、水素化精製触媒の分解反応に対する活性（分解活性）を十分に抑制することができず、生成油における中間留分収率、特に軽油留分収率を向上することが困難となる傾向にある。一方、炭素質物質の含有量が１質量％を超える場合には、水素化精製触媒の水素化異性化に対する活性（異性化活性）の低下が顕著になり、生成する中間留分、特に軽油留分の低温流動性を維持するためには水素化精製の反応温度を高くする必要があり、触媒の寿命が短縮される傾向にある。   When the content of the carbonaceous material in the catalyst is less than 0.05% by mass, the activity (decomposition activity) of the hydrorefining catalyst with respect to the decomposition reaction cannot be sufficiently suppressed, so It tends to be difficult to improve the fraction yield, particularly the diesel oil fraction yield. On the other hand, when the content of the carbonaceous substance exceeds 1% by mass, the hydrorefining catalyst's activity for hydroisomerization (isomerization activity) is significantly reduced, and the middle distillate produced, particularly the light oil distillate, is reduced. In order to maintain the low temperature fluidity of the minute, it is necessary to increase the reaction temperature of the hydrorefining, and the life of the catalyst tends to be shortened.

なお、水素化精製触媒中の炭素質物質の定量方法としては、当該水素化精製触媒の試料を酸素気流中、高周波により加熱して炭素質物質を燃焼させ、燃焼ガス中の二酸化炭素を、赤外線吸収を利用した検出器により定量する方法（例えば堀場製作所社製炭素・硫黄分析装置ＥＭＩＡ−９２０Ｖによる。）を採用する。   As a method for quantifying the carbonaceous material in the hydrotreating catalyst, a sample of the hydrotreating catalyst is heated at high frequency in an oxygen stream to burn the carbonaceous material, and carbon dioxide in the combustion gas is converted into infrared rays. A method of quantifying with a detector using absorption (for example, using a carbon / sulfur analyzer EMIA-920V manufactured by Horiba, Ltd.) is employed.

次に、本実施形態の水素化精製触媒を製造する方法について、２つの態様を例として以下に説明する。   Next, the method for producing the hydrorefining catalyst of the present embodiment will be described below by taking two aspects as examples.

まず、本実施形態の水素化精製触媒を製造する方法の第１実施形態について説明する。第１実施形態の方法は、水素化精製触媒を構成する担体の成型時に配合する成型助剤を有機化合物源として利用し、水素化精製触媒中に所定量の炭素質物質を含有せしめる方法である。   First, a first embodiment of a method for producing a hydrorefining catalyst of this embodiment will be described. The method of the first embodiment is a method in which a molding aid blended at the time of molding a carrier constituting the hydrotreating catalyst is used as an organic compound source, and a predetermined amount of carbonaceous material is contained in the hydrotreating catalyst. .

はじめに、上述の固体酸性を有する非晶性複合金属酸化物又はそのゲルと、上述のバインダと、成型助剤及び必要に応じて水等の液体からなる混合物を混練し、粘土状の捏和物を調製する。   First, a mixture of the above-mentioned amorphous mixed metal oxide having solid acidity or gel thereof, the above-mentioned binder, a molding aid and, if necessary, a liquid such as water is kneaded to obtain a clay-like kneaded product. To prepare.

ここで成型助剤とは、捏和物の成型性及び得られる成型された担体の機械的強度を向上させるために配合される有機化合物である。成型助剤としては特に限定されないが、前記成型助剤を配合する効果を十分に得るために、結晶性セルロース、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリビニルアルコール、澱粉、リグニン等の分子量が大きな有機化合物が好ましい。この成型助剤は、従来の水素化精製触媒の製造においては、後述する担体の焼成時及び／又は触媒前駆体の焼成時に除去され、得られる触媒には成型助剤由来の炭素質物質は残存しない。一方、本実施形態の水素化精製触媒を製造する方法の第１実施形態においては、担体の焼成時及び触媒前駆体の焼成時の焼成条件を調整することにより、成型助剤として配合した有機化合物由来の炭素質物質を触媒上に所定量残留させる。   Here, the molding aid is an organic compound blended to improve the moldability of the kneaded product and the mechanical strength of the resulting molded carrier. Although it does not specifically limit as a shaping | molding adjuvant, In order to fully acquire the effect which mix | blends the said shaping | molding adjuvant, organic compounds with large molecular weight, such as crystalline cellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, starch, lignin Is preferred. In the production of the conventional hydrorefining catalyst, this molding aid is removed at the time of calcining the support and / or the catalyst precursor, which will be described later, and the carbonaceous material derived from the molding aid remains in the resulting catalyst. do not do. On the other hand, in the first embodiment of the method for producing a hydrorefining catalyst of the present embodiment, an organic compound blended as a molding aid by adjusting the firing conditions at the time of firing the support and the catalyst precursor. A predetermined amount of the derived carbonaceous material is left on the catalyst.

なお、炭素質物質の由来源である有機化合物は、必ずしも前記成型助剤である必要はなく、所定量の炭素質物質を触媒中に生成することができるものであれば、その他の有機化合物であってもよい。しかし、成型助剤由来の炭素質物質を所定量残留させる方法を採用することで、後述する担体の焼成及び触媒前駆体の焼成条件を調整する以外は、従来の触媒調製の方法を大きく変更することなく本実施形態の水素化精製触媒を得ることができるため、この方法が好ましく採用される。   Note that the organic compound that is the source of the carbonaceous material is not necessarily the molding aid, and may be any other organic compound as long as it can generate a predetermined amount of the carbonaceous material in the catalyst. There may be. However, by adopting a method in which a predetermined amount of the carbonaceous material derived from the molding aid is retained, the conventional catalyst preparation method is greatly changed except for adjusting the calcining conditions of the carrier and the catalyst precursor described later. This method is preferably employed because the hydrorefining catalyst of this embodiment can be obtained without any problems.

成型助剤の配合量は、担体を構成する無機化合物（固体酸性を有する非晶性複合金属酸化物、バインダ及び場合により配合するその他の無機化合物）の合計の質量を基準として０．５〜１５質量％が好ましく、１〜１０質量％がより好ましい。   The blending amount of the molding aid is 0.5 to 15 on the basis of the total mass of the inorganic compound (amorphous composite metal oxide having solid acidity, binder and other inorganic compound optionally blended) constituting the carrier. % By mass is preferable, and 1 to 10% by mass is more preferable.

次に、上記捏和物を押出成型することにより成型物を得て、更に該成型物を例えば７０〜１５０℃にて乾燥する。   Next, a molded product is obtained by extrusion molding the kneaded product, and the molded product is further dried at 70 to 150 ° C., for example.

次に、乾燥された成型物を焼成することにより担体を得る。このとき、焼成条件としては、焼成により得られる担体の機械的強度が十分に発現し、且つ、担体上に成型助剤由来の炭素原子を含む残留物が適量残存するように選択する。ここで、成型助剤由来の炭素原子を含む残留物とは、担体の焼成の際に、成型助剤が酸化脱水素等の所謂「炭化」により分解して生成する、炭素原子若しくは炭素原子と水素原子及び／又は酸素原子等からなる炭素状の物質であり、前述の炭素質物質と同様の構造を有するもの、あるいは炭素質物質よりも炭化が進行していないものであって、後述の触媒前駆体の焼成によって、炭素質物質となるものを意味する。   Next, a carrier is obtained by baking the dried molding. At this time, the firing conditions are selected so that the mechanical strength of the carrier obtained by firing is sufficiently expressed, and an appropriate amount of the residue containing carbon atoms derived from the molding aid remains on the carrier. Here, the carbon-containing residue derived from the molding aid is a carbon atom or a carbon atom produced by decomposition of the molding aid by so-called “carbonization” such as oxidative dehydrogenation when the carrier is baked. A carbonaceous material composed of hydrogen atoms and / or oxygen atoms, etc., having a structure similar to that of the above-mentioned carbonaceous material, or one that is less carbonized than the carbonaceous material, It means what becomes a carbonaceous material by firing the precursor.

前記の要件を満たすための担体の焼成条件としては、種々の焼成温度と焼成時間との組み合わせを設定することができる。このとき、配合する成型助剤の量を考慮することが好ましい。例えば、焼成温度としては、３００〜５５０℃の範囲が好ましく、３５０〜５００℃の範囲がより好ましい。また、焼成時間としては、０．１〜１０時間程度の範囲が好ましく、０．２〜８時間程度の範囲がより好ましい。   As the firing conditions of the carrier for satisfying the above requirements, combinations of various firing temperatures and firing times can be set. At this time, it is preferable to consider the amount of the molding aid to be blended. For example, as a calcination temperature, the range of 300-550 degreeC is preferable, and the range of 350-500 degreeC is more preferable. Moreover, as a baking time, the range of about 0.1 to 10 hours is preferable, and the range of about 0.2 to 8 hours is more preferable.

次に、上述のようにして得られた担体に、上述の活性金属元素を含む化合物を担持する。担持に使用されるこれらの貴金属元素を含む化合物としては、当該貴金属元素を含むものであれば特に限定されず、公知の化合物が使用されるが、溶媒、特に水に可溶な無機又は有機化合物が利用される。活性金属元素を含む化合物の具体的な例としては、貴金属がルテニウムである場合にはＲｕＣｌ３など、貴金属がオスミウムである場合にはＯｓＣｌ３・３Ｈ２Ｏ、（ＮＨ４）２［ＯｓＣｌ６］など、貴金属がロジウムである場合にはＲｈＣｌ３・３Ｈ２Ｏなど、貴金属がイリジウムである場合にはＨ２ＩｒＣｌ６・６Ｈ２ＯＨなど、貴金属がパラジウムである場合には（ＮＨ４）２ＰｄＣｌ６、Ｐｄ（ＮＨ３）４Ｃｌ２・Ｈ２ＯおよびＰｄ（Ｃ２Ｈ５ＣＯ２）２など、貴金属が白金である場合にはＰｔＣｌ２、Ｈ２ＰｔＣｌ６、（ＮＨ４）２ＰｔＣｌ６、Ｈ２Ｐｔ（ＯＨ）６、Ｐｔ（ＮＨ３）４Ｃｌ２・Ｈ２ＯおよびＰｔ（Ｃ５Ｈ７Ｏ２）２などが挙げられる。 Next, the above-mentioned active metal element-containing compound is supported on the carrier obtained as described above. The compound containing these noble metal elements used for supporting is not particularly limited as long as it contains the noble metal element, and known compounds are used, but inorganic or organic compounds that are soluble in a solvent, particularly water. Is used. Specific examples of the compound containing an active metal element include RuCl 3 when the noble metal is ruthenium, and OsCl 3 .3H 2 O and (NH 4 ) 2 [OsCl 6 ] when the noble metal is osmium. Such as RhCl 3 .3H 2 O when the noble metal is rhodium, H 2 IrCl 6 .6H 2 OH when the noble metal is iridium, and (NH 4 ) 2 PdCl when the noble metal is palladium. 6 , Pd (NH 3 ) 4 Cl 2 .H 2 O and Pd (C 2 H 5 CO 2 ) 2, such as PtCl 2 , H 2 PtCl 6 , (NH 4 ) 2 PtCl 6 when the noble metal is platinum. , H 2 Pt (OH) 6 , Pt (NH 3 ) 4 Cl 2 .H 2 O, Pt (C 5 H 7 O 2 ) 2 and the like.

これらの活性金属元素を含む化合物の担持は、公知の方法により行なうことができる。すなわち、前記化合物の溶液、好ましくは水溶液により前記成形された担体を含浸する方法、イオン交換する方法などが好ましく利用される。含浸法としては特に限定されず、Ｉｎｃｉｐｉｅｎｔ Ｗｅｔｎｅｓｓ法などが好ましく利用される。   The loading of the compound containing these active metal elements can be performed by a known method. That is, a method of impregnating the shaped carrier with a solution of the compound, preferably an aqueous solution, a method of ion exchange, and the like are preferably used. The impregnation method is not particularly limited, and the Incipient Wetness method is preferably used.

次に、前記方法により活性金属元素を含む化合物が担持された担体を乾燥する。乾燥は例えば７０〜１５０℃程度の温度で行なうことができる。   Next, the carrier on which the compound containing the active metal element is supported is dried by the above method. Drying can be performed at a temperature of about 70 to 150 ° C., for example.

このようにして得られた活性金属元素を含む化合物成分が担持された担体（以下、「触媒前駆体」ということもある。）を焼成して、本実施形態の水素化精製触媒を得る。前記触媒前駆体の焼成においては、担体に担持された活性金属元素を含む化合物から活性金属原子以外の成分、すなわち対イオン、配位子等を除去するとともに、成型助剤由来の炭素質物質の含有量を、炭素原子換算で０．０５〜１質量％とする。   The thus-obtained carrier (hereinafter sometimes referred to as “catalyst precursor”) on which the compound component containing the active metal element is supported is calcined to obtain the hydrorefining catalyst of the present embodiment. In the firing of the catalyst precursor, components other than active metal atoms, that is, counter ions, ligands, and the like are removed from the compound containing the active metal element supported on the carrier, and the carbonaceous material derived from the molding aid is removed. Content is made into 0.05-1 mass% in conversion of a carbon atom.

前記触媒前駆体の焼成条件は、種々の焼成温度と焼成時間との組み合わせを設定することができる。このとき、前記担体の焼成において担体上に形成された成型助剤由来の炭素原子を含む残留物の含有量を考慮することが好ましい。例えば、焼成温度は、３００〜５５０℃の範囲が好ましく、３５０〜５３０℃の範囲がより好ましい。また、焼成時間としては、０．１〜１０時間程度の範囲が好ましく、０．２〜８時間程度の範囲がより好ましい。   As the firing conditions for the catalyst precursor, combinations of various firing temperatures and firing times can be set. At this time, it is preferable to consider the content of the residue containing carbon atoms derived from the molding aid formed on the support in the baking of the support. For example, the firing temperature is preferably in the range of 300 to 550 ° C, more preferably in the range of 350 to 530 ° C. Moreover, as a baking time, the range of about 0.1 to 10 hours is preferable, and the range of about 0.2 to 8 hours is more preferable.

なお、白金、パラジウム等の貴金属は、酸化反応に対する触媒活性を有する。そのため、触媒前駆体の焼成においては、比較的低い温度においても、触媒前駆体に含まれる成型助剤由来の炭素原子を含む残留物の酸化が進行しやすい。そして、この酸化の反応熱により触媒前駆体の実質的な温度が上昇し、前記酸化が急激に進行する、すなわち前記残留物が燃焼することがある。この場合、得られる触媒中の炭素質物質の含有量を制御することができず、炭素質物質が全て消失するか、あるいは所定の値よりも小さい含有量の炭素質物質を含む触媒が得られる傾向にある。更にこの場合、燃焼熱により触媒前駆体の実質的な温度が設定した焼成温度を大きく超えて上昇することにより、活性金属が凝集して、得られる触媒の活性が低下する傾向にある。このような急激な酸化反応の発生を防止するためには、触媒前駆体の焼成においては、少なくともその初期において、成型助剤由来の炭素原子を含む残留物の急激な酸化を抑制し、酸化が緩やかに進行する条件を選択することが好ましい。具体的には、焼成を行なうための加熱装置に触媒前駆体を仕込み、設定された焼成温度まで昇温する際に、少なくとも前記残留物の酸化が進行する温度範囲（例えば２５０〜４００℃程度）において、昇温速度を十分に小さくし、昇温の過程で前記急激な酸化反応が生起されないようにすることが好ましい。このような昇温速度としては、例えば、１〜５０℃／ｈであり、好ましくは５〜３０℃／ｈ程度である。   Note that noble metals such as platinum and palladium have catalytic activity for the oxidation reaction. Therefore, in the baking of the catalyst precursor, the oxidation of the residue containing carbon atoms derived from the molding aid contained in the catalyst precursor easily proceeds even at a relatively low temperature. Then, the substantial temperature of the catalyst precursor rises due to the reaction heat of the oxidation, and the oxidation proceeds rapidly, that is, the residue may burn. In this case, the content of the carbonaceous material in the obtained catalyst cannot be controlled, and all of the carbonaceous material disappears or a catalyst containing a carbonaceous material having a content smaller than a predetermined value is obtained. There is a tendency. Furthermore, in this case, when the substantial temperature of the catalyst precursor rises greatly exceeding the set firing temperature due to the heat of combustion, the active metal tends to aggregate and the activity of the resulting catalyst tends to decrease. In order to prevent the occurrence of such a rapid oxidation reaction, in the firing of the catalyst precursor, at least at the initial stage, rapid oxidation of the residue containing carbon atoms derived from the molding aid is suppressed, and oxidation is performed. It is preferable to select conditions that proceed slowly. Specifically, a temperature range (for example, about 250 to 400 ° C.) where at least oxidation of the residue proceeds when the catalyst precursor is charged into a heating device for performing firing and the temperature is raised to a set firing temperature. In this case, it is preferable to make the rate of temperature rise sufficiently low so that the rapid oxidation reaction does not occur in the course of temperature rise. As such a temperature rising rate, it is 1-50 degreeC / h, for example, Preferably it is about 5-30 degreeC / h.

また、触媒前駆体の焼成を２段階で行うことも好ましい。すなわち、第１の段階では前記残留物の酸化が緩やかに進行するよう、より低温の条件にて焼成を行い、酸化が進行して、急激な酸化が進行しない程度まで前記残留物の残存量が減少した段階で、第２の段階としてより高温の条件にて焼成を行い、触媒中の炭素質物質の含有量を制御する方法である。この場合、第１の段階の焼成温度としては、例えば２５０〜４００℃の範囲、第２の焼成温度としては例えば３５０〜５５０℃の範囲が選択される。   Moreover, it is also preferable to perform the firing of the catalyst precursor in two stages. That is, in the first stage, baking is performed at a lower temperature so that the oxidation of the residue proceeds slowly, and the remaining amount of the residue is reduced to such an extent that oxidation proceeds and rapid oxidation does not proceed. In the reduced stage, as a second stage, firing is performed under higher temperature conditions to control the content of the carbonaceous substance in the catalyst. In this case, as the firing temperature in the first stage, for example, a range of 250 to 400 ° C. is selected, and as the second firing temperature, for example, a range of 350 to 550 ° C. is selected.

以上のようにして、本実施形態の水素化精製触媒を得ることができる。   As described above, the hydrorefining catalyst of this embodiment can be obtained.

次に、本実施形態の水素化精製触媒を製造する方法の第２実施形態について説明する。第２実施形態の方法は、一旦従来の方法により炭素質物質を含まない水素化精製触媒を調製し、該触媒を有機化合物中に浸漬した後、これを加熱処理することにより、該触媒に所定量の炭素質物質を含有せしめる方法である。   Next, a second embodiment of the method for producing the hydrorefining catalyst of this embodiment will be described. According to the method of the second embodiment, a hydrorefining catalyst that does not contain a carbonaceous material is prepared once by a conventional method, and the catalyst is immersed in an organic compound, and then heated to treat the catalyst. This is a method of containing a certain amount of carbonaceous material.

まず、上述の固体酸性を有する非晶性複合金属酸化物又はそのゲルと、上述のバインダと、必要に応じて水等の液体からなる混合物を混練し、粘土状の捏和物を調製する。このとき、上述の第１実施形態の方法と同様に、成型助剤を配合してもよい。そして上述の第１実施形態の方法と同様の操作により担体の成型、乾燥を行なう。   First, a mixture of the above-described amorphous mixed metal oxide having solid acidity or a gel thereof, the above-mentioned binder, and a liquid such as water as necessary is kneaded to prepare a clay-like kneaded product. At this time, you may mix | blend a shaping | molding adjuvant like the method of the above-mentioned 1st Embodiment. Then, the carrier is molded and dried by the same operation as the method of the first embodiment described above.

次に、得られた乾燥された成型物を焼成して担体を得る。前記捏和物を調製する工程において成型助剤を配合する場合は、担体を焼成するときに、後段での触媒前駆体（担体に活性金属元素を含む化合物を担持したもの）の焼成において前述の急激な酸化が生起されない程度に、成型助剤に由来する炭素原子を含む残留物の残存量を低減することが好ましい。或いは、前記残留物が消失するように焼成を行なってもよい。   Next, the obtained dried molded product is fired to obtain a carrier. When a molding aid is blended in the step of preparing the kneaded product, when the support is fired, the catalyst precursor (which carries the compound containing the active metal element on the support) is calcined at the later stage. It is preferable to reduce the residual amount of the residue containing carbon atoms derived from the molding aid to such an extent that rapid oxidation does not occur. Alternatively, baking may be performed so that the residue disappears.

このような担体の焼成条件としては、種々の焼成温度と焼成時間との組み合わせを設定することができる。このとき、配合する成型助剤の量を考慮することが好ましい。例えば、焼成温度としては、３００〜６００℃の範囲が好ましく、３５０〜５５０℃の範囲がより好ましい。また、焼成時間としては、０．１〜１０時間程度の範囲が好ましく、０．２〜８時間程度の範囲がより好ましい。   As such carrier firing conditions, combinations of various firing temperatures and firing times can be set. At this time, it is preferable to consider the amount of the molding aid to be blended. For example, as a calcination temperature, the range of 300-600 degreeC is preferable, and the range of 350-550 degreeC is more preferable. Moreover, as a baking time, the range of about 0.1 to 10 hours is preferable, and the range of about 0.2 to 8 hours is more preferable.

このようにして担体が得られる。   A carrier is thus obtained.

次に、上記のようにして得られた担体に活性金属元素を含む化合物を担持し、更に乾燥を行なう。この活性金属元素を含む化合物の担持及び乾燥は、上述の第１実施形態の方法と同様にして行なうことができる。このようにして触媒前駆体が得られる。   Next, the carrier obtained as described above is loaded with a compound containing an active metal element and further dried. The loading and drying of the compound containing the active metal element can be performed in the same manner as the method of the first embodiment described above. In this way, a catalyst precursor is obtained.

次に得られた触媒前駆体を焼成して触媒を得る。触媒前駆体を焼成する条件は、従来の水素化精製触媒の前駆体の焼成条件と同様であってよく、例えば焼成温度は３５０〜６００℃、焼成時間は０．５〜１０時間程度である。この段階の触媒を以下、「予備触媒」ということもある。   Next, the obtained catalyst precursor is calcined to obtain a catalyst. The conditions for calcining the catalyst precursor may be the same as those for the conventional hydrorefining catalyst precursor. For example, the calcining temperature is 350 to 600 ° C., and the calcining time is about 0.5 to 10 hours. Hereinafter, the catalyst at this stage may be referred to as “preliminary catalyst”.

このようにして得られた予備触媒を液状の有機化合物に浸漬する。液状の有機化合物としては、触媒毒となる硫黄分、窒素分、ハロゲン分等を含まないものであれば特に限定されないが、液状の炭化水素であることが好ましく、例えばＧＴＬプロセスにより製造されたナフサ留分、灯油留分、軽油留分等が好適に使用される。触媒をこれらの液状の有機化合物に浸漬する方法は特に限定されない。   The precatalyst thus obtained is immersed in a liquid organic compound. The liquid organic compound is not particularly limited as long as it does not contain sulfur, nitrogen, halogen, etc., which are catalyst poisons, but is preferably a liquid hydrocarbon, for example, naphtha produced by the GTL process. A fraction, a kerosene fraction, a light oil fraction and the like are preferably used. The method for immersing the catalyst in these liquid organic compounds is not particularly limited.

液状の有機化合物に浸漬した予備触媒を該有機化合物中から取り出し、不活性ガス、好ましくは窒素ガス中で脱油処理を行う。この脱油処理により、浸漬によって予備触媒に付着した過剰な有機化合物が揮散する。脱油処理の条件は、浸漬する有機化合物等によって変化することから一概にいうことはできないが、温度は１８０〜５００℃程度、時間は０．１〜１０時間程度である。   The pre-catalyst immersed in the liquid organic compound is taken out from the organic compound and deoiled in an inert gas, preferably nitrogen gas. By this deoiling treatment, excess organic compounds attached to the pre-catalyst by immersion are volatilized. The conditions for the deoiling treatment vary depending on the organic compound and the like to be immersed, but cannot be generally stated, but the temperature is about 180 to 500 ° C. and the time is about 0.1 to 10 hours.

次に、脱油処理された予備触媒を、分子状酸素を含む雰囲気下、好ましくは空気雰囲気下に加熱処理（焼成）して、予備触媒に残留した例えば軽油等の上記有機化合物を炭化させて、炭素質物質を生成させる。焼成条件は、使用する有機化合物、脱油処理後に予備触媒に残留する有機化合物の含有量、触媒に含有せしめる炭素質物質の含有量等に応じて適宜設定することができる。例えば、焼成温度は、３００〜５５０℃の範囲が好ましく、３５０〜５３０℃がより好ましい。焼成時間は、０．１〜１０時間程度が好ましく、０．２〜８時間程度がより好ましい。こうして、触媒中に炭素質物質を、その含有量が炭素原子換算で０．０５〜１質量％となるように生成させる。   Next, the deoiled pre-catalyst is heat-treated (calcined) in an atmosphere containing molecular oxygen, preferably in an air atmosphere, to carbonize the organic compound such as light oil remaining in the pre-catalyst. To produce a carbonaceous material. Firing conditions can be appropriately set according to the organic compound to be used, the content of the organic compound remaining in the pre-catalyst after the deoiling treatment, the content of the carbonaceous material to be contained in the catalyst, and the like. For example, the firing temperature is preferably in the range of 300 to 550 ° C, more preferably 350 to 530 ° C. The firing time is preferably about 0.1 to 10 hours, and more preferably about 0.2 to 8 hours. In this way, the carbonaceous material is produced in the catalyst so that the content is 0.05 to 1% by mass in terms of carbon atoms.

なお、上記の例では、触媒前駆体を焼成して得た予備触媒を有機化合物中に浸漬し、脱油処理後に再度焼成して本実施形態の水素化精製触媒を得たが、触媒前駆体の焼成は行なわず、触媒前駆体を有機化合物中に浸漬し、脱油処理の後に一度の焼成により水素化精製触媒を得てもよい。   In the above example, the preliminary catalyst obtained by calcining the catalyst precursor was immersed in an organic compound, and calcined again after deoiling treatment to obtain the hydrorefining catalyst of this embodiment. The hydrotreating catalyst may be obtained by immersing the catalyst precursor in an organic compound and performing a single firing after the deoiling treatment.

以上のようにして、本実施形態の水素化精製触媒を得ることができる。   As described above, the hydrorefining catalyst of this embodiment can be obtained.

次に、本発明の炭化水素油の製造方法について説明する。   Next, the manufacturing method of the hydrocarbon oil of this invention is demonstrated.

本発明の炭化水素油の製造方法は、上述の本発明の水素化精製触媒に、分子状水素の共存下、沸点が２５〜３６０℃の範囲にある直鎖状脂肪族炭化水素を８０質量％以上含み且つ沸点が１５０〜３６０℃の範囲にある直鎖状脂肪族炭化水素を２０質量％以上含む原料油を接触させる工程を有する。この工程により原料油の水素化精製、すなわち前記原料油中に含まれる不純物であるオレフィン類及び含酸素化合物の除去、並びに直鎖状脂肪族炭化水素の水素化異性化が行われる。   The method for producing a hydrocarbon oil of the present invention comprises 80% by mass of a linear aliphatic hydrocarbon having a boiling point in the range of 25 to 360 ° C. in the presence of molecular hydrogen in the hydrorefining catalyst of the present invention. The step of bringing into contact a raw material oil containing 20% by mass or more of a linear aliphatic hydrocarbon having a boiling point in the range of 150 to 360 ° C. is included. By this step, hydrorefining of the feedstock, that is, removal of olefins and oxygen-containing compounds which are impurities contained in the feedstock, and hydroisomerization of the linear aliphatic hydrocarbons are performed.

以下、本発明の炭化水素油の製造方法が好ましく利用されるＧＴＬプロセスの例に沿って、本発明の炭化水素油の製造方法の実施形態について説明を行なう。   Hereinafter, along with an example of a GTL process in which the method for producing hydrocarbon oil of the present invention is preferably used, an embodiment of the method for producing hydrocarbon oil of the present invention will be described.

図１は、本発明の炭化水素油の製造方法の一実施形態が実施される炭化水素油の製造装置を含む、ＧＴＬプロセスにおけるアップグレーディングユニットに相当する製造設備を示す概略構成図である。   FIG. 1 is a schematic configuration diagram showing a production facility corresponding to an upgrade unit in a GTL process, including a hydrocarbon oil production apparatus in which an embodiment of the hydrocarbon oil production method of the present invention is implemented.

まず、図１を参照して、本発明の炭化水素油の製造方法の好適な実施形態が実施される、ＦＴ合成反応によって得られる炭化水素（ＦＴ合成油）から、ナフサ、灯油・軽油基材を製造する装置について説明する。   First, referring to FIG. 1, a naphtha, kerosene / light oil base material is obtained from a hydrocarbon (FT synthetic oil) obtained by an FT synthesis reaction in which a preferred embodiment of the method for producing a hydrocarbon oil of the present invention is carried out. The apparatus which manufactures will be described.

図１に示される炭化水素油の製造装置１００は、合成ガス（一酸化炭素ガスと水素ガスの混合ガス）を原料として、ＦＴ合成反応により炭化水素油（ＦＴ合成油）を合成するＦＴ合成反応装置（図示省略。）から、ライン１を経てＦＴ合成油の供給を受ける。なお、ＦＴ合成反応装置は、天然ガスを改質して合成ガスを製造する改質反応装置（図示省略。）から合成ガスの供給を受ける。   The hydrocarbon oil production apparatus 100 shown in FIG. 1 uses a synthesis gas (mixed gas of carbon monoxide gas and hydrogen gas) as a raw material to synthesize a hydrocarbon oil (FT synthesis oil) by an FT synthesis reaction. FT synthetic oil is supplied from a device (not shown) via line 1. The FT synthesis reaction apparatus is supplied with synthesis gas from a reforming reaction apparatus (not shown) that reforms natural gas to produce synthesis gas.

炭化水素油の製造装置１００は、ＦＴ合成油を粗ナフサ留分、粗中間留分及び粗ワックス留分に分留する第１精留塔２０と、第１精留塔２０の塔頂からライン２により供給される粗ナフサ留分を水素化精製するナフサ留分水素化精製反応装置３０と、第１精留塔２０の中央部からライン３により供給される粗中間留分を水素化精製及び水素化異性化する中間留分水素化精製反応器３２と、第１精留塔２０の底部からライン４により供給される粗ワックス留分を水素化分解するワックス留分水素化分解反応器３４と、中間留分の水素化精製物及びワックス留分の水素化分解物を分留する第２精留塔６０を主として備えている。   The hydrocarbon oil production apparatus 100 includes a first rectifying column 20 that fractionates FT synthetic oil into a crude naphtha fraction, a crude middle distillate, and a crude wax fraction, and a line from the top of the first rectifying column 20. Hydrorefining the naphtha fraction hydrotreating reaction apparatus 30 for hydrotreating the crude naphtha fraction supplied by 2, and hydrotreating the crude middle distillate supplied by the line 3 from the center of the first rectifying column 20. A middle fraction hydrotreating reactor 32 for hydroisomerization, a wax fraction hydrocracking reactor 34 for hydrocracking the crude wax fraction supplied from the bottom of the first fractionator 20 via line 4; The second fractionator 60 mainly fractionates the hydrofinished product of the middle fraction and the hydrocracked product of the wax fraction.

ここで、ナフサ留分は、概ね２５℃以上であり概ね１５０℃よりも低い沸点を有する（概ねＣ５〜Ｃ１０）炭化水素留分であり、中間留分は沸点が概ね１５０〜３６０℃である（概ねＣ１１〜Ｃ２１）炭化水素留分であり、ワックス留分は沸点が概ね３６０℃を越える（概ねＣ２２以上）炭化水素留分である。また、粗ナフサ留分、粗中間留分及び粗ワックス留分は、それぞれ水素化精製又は水素化分解を受けておらず、飽和脂肪族炭化水素（パラフィン）以外の不純物（ＦＴ合成反応の副生成物）であるオレフィン類及びアルコール類等の含酸素化合物を含むそれぞれの前記留分を意味する。 Here, the naphtha fraction is a hydrocarbon fraction having a boiling point of approximately 25 ° C. or higher and generally lower than 150 ° C. (approximately C 5 to C 10 ), and the middle fraction has a boiling point of approximately 150 to 360 ° C. There are certain (approximately C 11 to C 21 ) hydrocarbon fractions, and the wax fraction is a hydrocarbon fraction having a boiling point generally exceeding 360 ° C. (approximately C 22 or more). The crude naphtha fraction, crude middle fraction, and crude wax fraction have not been subjected to hydrorefining or hydrocracking, respectively, and impurities other than saturated aliphatic hydrocarbons (paraffins) (by-products of the FT synthesis reaction) Each of the above-mentioned fractions containing oxygen-containing compounds such as olefins and alcohols.

中間留分水素化精製反応器３２は、本実施形態の炭化水素油の製造方法を実施する装置であり、その内部に、好ましくは固定床として、上記本実施形態の水素化精製触媒が充填されている。ライン３により供給される粗中間留分は、ライン３に接続する水素ガス供給ライン（図示省略。）により供給される水素ガスと混合され、ライン３上に配設された熱交換器等の加熱手段（図示省略。）により反応温度まで加熱された後、中間留分水素化精製反応器３２に供給され、水素化異性化を含む水素化精製が施される。   The middle distillate hydrotreating reactor 32 is an apparatus for carrying out the hydrocarbon oil production method of the present embodiment, and the hydrotreating catalyst of the present embodiment is filled therein, preferably as a fixed bed. ing. The crude middle distillate supplied by the line 3 is mixed with hydrogen gas supplied by a hydrogen gas supply line (not shown) connected to the line 3 and heated by a heat exchanger or the like disposed on the line 3. After being heated to the reaction temperature by means (not shown), it is supplied to the middle distillate hydrorefining reactor 32 and subjected to hydrorefining including hydroisomerization.

ナフサ留分水素化精製反応装置３０には好ましくは固定床として、水素化精製触媒が充填されている。該水素化精製触媒は、上記本実施形態の水素化精製触媒であってもよい。ライン２により供給される粗ナフサ留分は、ライン２に接続する水素ガス供給ライン（図示省略。）により供給される水素ガスと混合され、ライン２上に配設された熱交換器等の加熱手段（図示省略。）により反応温度まで加熱された後、ナフサ留分水素化精製反応器３０に供給され、水素化精製される。   The naphtha fraction hydrotreating reactor 30 is preferably packed with a hydrotreating catalyst as a fixed bed. The hydrotreating catalyst may be the hydrotreating catalyst of the present embodiment. The crude naphtha fraction supplied by the line 2 is mixed with hydrogen gas supplied by a hydrogen gas supply line (not shown) connected to the line 2 and heated by a heat exchanger or the like disposed on the line 2. After being heated to the reaction temperature by means (not shown), it is supplied to the naphtha fraction hydrotreating reactor 30 for hydrotreating.

ワックス留分水素化分解反応器３４には、好ましくは固定床として、水素化分解触媒が充填されている。ライン４により供給される粗ワックス留分は、ライン４に接続するライン１３によりリサイクルされる未分解ワックス（詳細は後述）及びライン４に接続する水素ガス供給ライン（図示省略。）により供給される水素ガスと混合され、ライン４上に配設される熱交換器等の加熱手段（図示省略。）により反応温度まで加熱された後、ワックス留分水素化分解反応器３４に供給され、水素化分解される。   The wax fraction hydrocracking reactor 34 is preferably packed with a hydrocracking catalyst as a fixed bed. The crude wax fraction supplied by the line 4 is supplied by an undecomposed wax (details will be described later) recycled by a line 13 connected to the line 4 and a hydrogen gas supply line (not shown) connected to the line 4. After being mixed with hydrogen gas and heated to a reaction temperature by a heating means such as a heat exchanger (not shown) disposed on the line 4, it is supplied to the wax fraction hydrocracking reactor 34 for hydrogenation. Disassembled.

炭化水素油の製造装置１００は、ナフサ留分水素化精製反応装置３０、中間留分水素化精製反応装置３２及びワックス留分水素化分解反応器３４の下流に、それぞれ気液分離器４０、４２及び４４を備え、それぞれの反応装置から排出される水素化精製物又は水素化分解物である液体炭化水素と、未反応の水素ガス及びガス状の炭化水素を含む気体成分とを気液分離する。また、それぞれの気液分離器には、水素化精製又は水素化分解時に副生する水を排出するための装置（図示省略。）が付随する。   The hydrocarbon oil production apparatus 100 includes gas-liquid separators 40 and 42 downstream of the naphtha fraction hydrotreating reactor 30, the middle distillate hydrotreating reactor 32, and the wax fraction hydrocracking reactor 34, respectively. And 44 for gas-liquid separation of liquid hydrocarbons that are hydrorefined products or hydrocracked products discharged from the respective reactors and gaseous components containing unreacted hydrogen gas and gaseous hydrocarbons . Each gas-liquid separator is accompanied by a device (not shown) for discharging water produced as a by-product during hydrorefining or hydrocracking.

炭化水素油の製造装置１００は、気液分離器４０の下流に、ライン５を介して供給される水素化精製されたナフサ留分から、炭素数４以下の炭化水素を主成分とするガス状炭化水素を、その塔頂に接続されたライン８から排出するナフサスタビライザー５０を備える。また、ナフサスタビライザー５０の塔底から、ライン９によりガス状炭化水素が除去されたナフサ留分が供給され、これを貯留するためのナフサタンク７０が備えられている。   The apparatus 100 for producing hydrocarbon oil is a gaseous carbonization mainly composed of a hydrocarbon having 4 or less carbon atoms from a hydrorefined naphtha fraction supplied via a line 5 downstream of the gas-liquid separator 40. A naphtha stabilizer 50 for discharging hydrogen from a line 8 connected to the top of the column is provided. A naphtha fraction from which gaseous hydrocarbons have been removed by a line 9 is supplied from the bottom of the naphtha stabilizer 50 and a naphtha tank 70 is provided for storing the naphtha fraction.

第２精留塔６０は、気液分離器４２及び気液分離器４４の下流に配設され、気液分離器４２からライン６を介して供給される水素化精製された中間留分と、気液分離器４４からライン７を介して供給されるワックス留分の水素化分解物とが供給され、これらの混合物を分留する。第２精留塔６０には、その中央部に接続され、分留された灯油留分を取り出し、灯油タンク７２に移送するためのライン１１、その下部に接続され、分留された軽油留分を取り出し、軽油タンク７４に移送するためのライン１２が設けられている。また、第２精留塔６０の塔底には、ワックス留分水素化分解反応装置３４内で十分に分解されなかった未分解ワクッスを主成分とする第２精留塔６０の塔底油を抜き出し、ワックス留分水素化分解反応装置３４の上流のライン４にリサイクルするためのライン１３が接続されている。更に第２精留塔６０の塔頂には、ナフサ留分を主な成分とする軽質炭化水素を抜き出し、ナフサスタビライザー５０に供給するライン１０が接続されている。   The second rectifying column 60 is disposed downstream of the gas-liquid separator 42 and the gas-liquid separator 44, and is subjected to hydrorefining middle distillate supplied from the gas-liquid separator 42 via the line 6, The hydrocracked product of the wax fraction fed from the gas-liquid separator 44 via the line 7 is fed to fractionate the mixture. The second fractionator 60 is connected to the center of the second fractionator 60. The fraction 11 of the kerosene fraction taken out and transferred to the kerosene tank 72 is connected to the lower part of the second fractionator, and the fraction of light oil fraction fractionated. A line 12 is provided for taking out the fuel and transferring it to the light oil tank 74. Further, the bottom oil of the second rectifying column 60 containing as a main component undecomposed wax that has not been sufficiently decomposed in the wax fraction hydrocracking reactor 34 is added to the bottom of the second rectifying column 60. A line 13 for extraction and recycling to the line 4 upstream of the wax fraction hydrocracking reactor 34 is connected. Further, a line 10 is connected to the top of the second rectifying column 60 for extracting light hydrocarbons mainly composed of a naphtha fraction and supplying the extracted light hydrocarbons to the naphtha stabilizer 50.

次に、図１を参照し、本発明の炭化水素油の製造方法の一実施形態について説明する。   Next, with reference to FIG. 1, one Embodiment of the manufacturing method of the hydrocarbon oil of this invention is described.

ＦＴ合成反応装置（図示省略。）よりライン１を経て供給されるＦＴ合成油は、第１精留塔２０において粗ナフサ留分、粗中間留分及び粗ワックス留分に分留される。分留された粗中間留分は、第１精留塔２０の中央部からライン３により抜き出される。中間留分は、一般的に沸点が概ね１５０〜３６０℃（概ねＣ１１〜Ｃ２１）である炭化水素混合物からなる留分である。ＦＴ合成油を分留して得られる粗中間留分は、前記沸点範囲をもつ直鎖状飽和脂肪族炭化水素を主成分とし、不純物として、ＦＴ合成反応の副生成物であるオレフィン類及びアルコール類等の含酸素化合物を含む。粗中間留分は水素ガスと混合された上で反応温度まで加熱され、中間留分水素化精製反応装置３２に供給される。該反応装置には、前述の本実施形態の水素化精製触媒が充填されており、粗中間留分と水素ガスとの混合物が該触媒と接触することにより、粗中間留分の水素化精製及び水素化異性化が進行する。 The FT synthetic oil supplied via the line 1 from the FT synthesis reaction apparatus (not shown) is fractionated into a crude naphtha fraction, a crude middle distillate, and a crude wax fraction in the first rectifying column 20. The fractionated crude middle distillate is extracted from the center of the first rectifying column 20 by the line 3. The middle distillate is generally a distillate consisting of a hydrocarbon mixture having a boiling point of approximately 150 to 360 ° C. (approximately C 11 to C 21 ). The crude middle distillate obtained by fractionating FT synthetic oil is mainly composed of linear saturated aliphatic hydrocarbons having the above boiling range, and as impurities, olefins and alcohols that are by-products of the FT synthesis reaction Including oxygen-containing compounds. The crude middle distillate is mixed with hydrogen gas, heated to the reaction temperature, and supplied to the middle distillate hydrotreating reactor 32. The reaction apparatus is filled with the hydrorefining catalyst of the above-described embodiment, and the mixture of the crude middle distillate and hydrogen gas is brought into contact with the catalyst, thereby hydrotreating the crude middle distillate and Hydroisomerization proceeds.

粗中間留分の水素化精製は、粗中間留分中に含まれる不純物（オレフィン類及びアルコール等の含酸素化合物）を除去する反応である。オレフィン類（不飽和脂肪族炭化水素類）は水素化されて飽和脂肪族炭化水素（パラフィン）に転化される。また、アルコール類等の含酸素化合物は水素化脱酸素されて、飽和脂肪族炭化水素と水等に転化される。   The hydrorefining of the crude middle distillate is a reaction that removes impurities (oxygen compounds such as olefins and alcohols) contained in the crude middle distillate. Olefins (unsaturated aliphatic hydrocarbons) are hydrogenated and converted to saturated aliphatic hydrocarbons (paraffins). In addition, oxygen-containing compounds such as alcohols are hydrodeoxygenated and converted into saturated aliphatic hydrocarbons and water.

水素化異性化は、直鎖状飽和脂肪族炭化水素（ノルマルパラフィン）を骨格異性化し、分枝鎖状飽和炭化水素（イソパラフィン）に転化する。水素化異性化により、中間留分中のノルマルパラフィンの含有量が低下し、イソパラフィンの含有量が増加することにより、パラフィンの結晶性が低下し、燃料油としての低温流動性が向上する。水素化異性化の進行の程度を判断するひとつの指標として、例えば、炭素数１８（Ｃ１８）の炭化水素（オクタデカン）における分枝鎖を有するオクタデカン（イソオクタデカン）の比率（１００×イソオクタデカンの質量／全オクタデカンの質量（％）、以下、「Ｃ１８異性体率」という。）を利用することができる。軽油基材としての低温流動性を満たすためには、例えばＣ１８異性体率が８５％以上であることが好ましい。 In the hydroisomerization, a linear saturated aliphatic hydrocarbon (normal paraffin) is skeletal isomerized and converted into a branched saturated hydrocarbon (isoparaffin). By hydroisomerization, the content of normal paraffin in the middle distillate is decreased, and the content of isoparaffin is increased, so that the crystallinity of paraffin is decreased and the low temperature fluidity as fuel oil is improved. As an index of one to determine the degree of progression of the hydroisomerization, for example, carbon 18 (C 18) hydrocarbon ratio (100 × iso octadecanoic octadecanoic having a branch chain in (octadecanoic) (iso-octadecane) Mass / mass of total octadecane (%), hereinafter referred to as “C 18 isomer ratio”). In order to satisfy the low temperature fluidity as a light oil base material, for example, the C 18 isomer ratio is preferably 85% or more.

本実施形態においては、例えばＣ１８異性体率で表される水素化異性化の進行の程度が基準を満たすように水素化異性化を行なうためには、主として中間留分水素化精製反応装置３２の反応温度を調整して運転を行う。 In the present embodiment, for example, in order to perform hydroisomerization so that the degree of progress of hydroisomerization represented by the C 18 isomer ratio satisfies the standard, the middle distillate hydrorefining reactor 32 is mainly used. Operate by adjusting the reaction temperature.

中間留分水素化精製反応装置３２における反応温度は１８０〜４００℃、好ましくは２００〜３７０℃、更に好ましくは２５０〜３５０℃、特に好ましくは２８０〜３４０℃である。ここで、反応温度とは、中間留分水素化精製反応装置２２内の触媒層の重量平均温度のことである。反応温度が４００℃を越えると、軽質分への分解が進行して中間留分の収率が減少するだけでなく、生成物が着色し、燃料油基材としての使用が制限される傾向にある。一方、反応温度が１８０℃を下回ると、アルコール類等の含酸素化合物が十分に除去されずに残存し、また、水素化異性化反応によるイソパラフィンの生成が抑制される傾向にある。   The reaction temperature in the middle distillate hydrotreating reactor 32 is 180 to 400 ° C, preferably 200 to 370 ° C, more preferably 250 to 350 ° C, and particularly preferably 280 to 340 ° C. Here, the reaction temperature is the weight average temperature of the catalyst layer in the middle distillate hydrotreating reactor 22. When the reaction temperature exceeds 400 ° C., decomposition to light components proceeds and not only the yield of middle distillate decreases, but also the product tends to be colored and its use as a fuel oil base tends to be limited. is there. On the other hand, when the reaction temperature is lower than 180 ° C., oxygen-containing compounds such as alcohols remain without being sufficiently removed, and the production of isoparaffins due to hydroisomerization tends to be suppressed.

中間留分水素化精製反応装置２２における圧力（水素分圧）は０．５〜１２ＭＰａであることが好ましく、１〜５ＭＰａであることがより好ましい。前記圧力が０．５ＭＰａ未満の場合には水素化精製及び水素化異性化が十分に進行しない傾向にあり、一方、１２ＭＰａを超える場合には装置に高い耐圧性が要求され、設備コストが上昇する傾向にある。   The pressure (hydrogen partial pressure) in the middle distillate hydrotreating reactor 22 is preferably 0.5 to 12 MPa, and more preferably 1 to 5 MPa. When the pressure is less than 0.5 MPa, hydrorefining and hydroisomerization tend not to proceed sufficiently. On the other hand, when the pressure exceeds 12 MPa, the apparatus is required to have high pressure resistance and the equipment cost increases. There is a tendency.

中間留分水素化精製反応装置２２における液空間速度（ＬＨＳＶ［liquid hourly space velocity］）は０．１〜１０ｈ−１であることが好ましく、０．３〜３．５ｈ−１であることがより好ましい。ＬＨＳＶが０．１ｈ−１未満の場合には軽質分への分解が進行して中間留分の収率が減少し、また生産性が低下する傾向にあり、一方、１０．０ｈ−１を超える場合には、水素化精製及び水素化異性化が十分に進行しない傾向にある。 Intermediate liquid hourly space velocity in the fraction hydrotreating reactor 22 (LHSV [liquid hourly space velocity ]) is more be preferably from 0.1 to 10 -1, is 0.3 to 3.5 -1 preferable. When LHSV is less than 0.1 h −1 , decomposition to light components proceeds and the yield of middle distillate tends to decrease, and productivity tends to decrease, whereas it exceeds 10.0 h −1 . In some cases, hydrorefining and hydroisomerization tend not to proceed sufficiently.

中間留分水素化精製反応装置３２における水素ガス／油比は５０〜１０００ＮＬ／Ｌであることが好ましく、７０〜８００ＮＬ／Ｌであることがより好ましい。ここで、「ＮＬ」とは、標準状態（０℃、１０１３２５Ｐａ）における水素容量（Ｌ）のことを意味する。水素ガス／油比が５０ＮＬ／Ｌ未満の場合には水素化精製及び水素化異性化が十分に進行しない傾向にあり、一方、１０００ＮＬ／Ｌを超える場合には、大規模な水素供給装置等が必要となる傾向にある。   The hydrogen gas / oil ratio in the middle distillate hydrotreating reactor 32 is preferably 50 to 1000 NL / L, and more preferably 70 to 800 NL / L. Here, “NL” means the hydrogen capacity (L) in the standard state (0 ° C., 101325 Pa). When the hydrogen gas / oil ratio is less than 50 NL / L, hydrorefining and hydroisomerization tend not to proceed sufficiently. On the other hand, when it exceeds 1000 NL / L, a large-scale hydrogen supply device or the like It tends to be necessary.

中間留分水素化精製反応装置３２においては、前述のように、粗中間留分の主成分である直鎖状飽和脂肪族炭化水素（ノルマルパラフィン）を分枝鎖状飽和炭化水素（イソパラフィン）へ転化する水素化異性化反応を行うが、生成油から得られる軽油留分の液体燃料基材としての低温流動性が規格を満たすためには、粗中間留分中のノルマルパラフィンの一定割合以上をイソパラフィンに転化する必要がある（例えばＣ１８異性体率が８５％以上とすることが好ましい。）。 In the middle distillate hydrotreating reactor 32, as described above, the straight chain saturated aliphatic hydrocarbon (normal paraffin), which is the main component of the crude middle distillate, is converted into the branched saturated hydrocarbon (isoparaffin). The hydroisomerization reaction to be converted is performed, but in order for the low temperature fluidity as the liquid fuel base of the light oil fraction obtained from the product oil to meet the standard, a certain percentage or more of normal paraffin in the crude middle distillate is required. It is necessary to convert to isoparaffin (for example, the C 18 isomer ratio is preferably 85% or more).

一方、粗中間留分の水素化精製においては、副反応として、炭化水素の分解反応（水素化分解反応）が生起される。この分解反応は、炭化水素の炭素−炭素結合を開裂し、炭素数の少ない炭化水素を生成する。したがって、この分解反応が優勢になると軽質炭化水素の生成が増加し、中間留分（沸点範囲が概ね１５０〜３６０℃）の収率、中でも軽油留分（沸点範囲が概ね２５０〜３６０℃）の収率が低下する。   On the other hand, in the hydrorefining of a crude middle distillate, a hydrocarbon decomposition reaction (hydrocracking reaction) occurs as a side reaction. This decomposition reaction cleaves the carbon-carbon bond of the hydrocarbon to produce a hydrocarbon having a small number of carbon atoms. Therefore, when this cracking reaction becomes dominant, the production of light hydrocarbons increases, and the yield of middle distillate (boiling point range is approximately 150 to 360 ° C.), especially light oil distillate (boiling point range is approximately 250 to 360 ° C.) Yield decreases.

水素化異性化反応は、水素化精製触媒中の活性金属による水素化−脱水素活性と、担体の固体酸性の二種の触媒機能により進行することが知られているが、水素化分解反応も同様に前記二種の触媒機能により進行する。したがって、従来の水素化精製触媒を用いて、生成油、特に軽油留分の低温流動性を確保するために水素化精製反応装置３２の反応温度を調整して、水素化異性化を一定水準まで進行させると、分解反応も同時に進行し、中間留分収率、特に軽油留分収率が低下する傾向にあった。より具体的には、例えば前述のＣ１８異性化率が８５％となるように中間留分水素化精製反応装置３２の反応温度を調整して粗中間留分の水素化精製を行なうと、副反応である分解反応が進行し、軽油留分（沸点範囲が例えば２５０〜３６０℃）の沸点範囲の下限を下回る軽質留分の生成が増加し、軽油留分の収率が低下する傾向にあった。 The hydroisomerization reaction is known to proceed by two types of catalytic functions, ie, the hydrogenation-dehydrogenation activity by the active metal in the hydrorefining catalyst and the solid acidity of the support. Similarly, the two types of catalytic functions proceed. Therefore, by using a conventional hydrorefining catalyst, the hydroisomerization is brought to a certain level by adjusting the reaction temperature of the hydrorefining reactor 32 in order to ensure the low temperature fluidity of the product oil, particularly the light oil fraction. As it proceeded, the cracking reaction proceeded simultaneously, and the middle distillate yield, particularly the light oil fraction yield, tended to decrease. More specifically, for example, when the crude middle distillate is hydrorefined by adjusting the reaction temperature of the middle distillate hydrotreating reactor 32 so that the C 18 isomerization rate is 85%, The cracking reaction, which is a reaction, progresses, and the production of light fractions below the lower limit of the boiling point range of light oil fractions (boiling point range: 250 to 360 ° C., for example) increases, and the yield of light oil fractions tends to decrease. It was.

これに対して、本実施形態の水素化精製触媒は上記特定の構成を有することにより高い水素化異性化活性と抑制された水素化分解活性を両立することができ、該触媒を用いることにより、高いＣ１８異性体率と高い中間留分収率、特に軽油留分収率とを同時に達成することができる。 On the other hand, the hydrorefining catalyst of the present embodiment can achieve both a high hydroisomerization activity and a suppressed hydrocracking activity by having the above specific configuration, and by using the catalyst, A high C18 isomer ratio and a high middle distillate yield, in particular a light oil fraction yield, can be achieved simultaneously.

このような本実施形態の水素化精製触媒のもつ特徴が発現される作用機構は定かではないが、本発明者らは以下のように推定している。すなわち、水素化精製触媒は、活性金属による水素化−脱水素能と、担体が有する固体酸性の２種の機能を有する。そして、水素化異性化反応及び副反応である水素化分解反応は、共に複合化された前記２種の機能により進行すると考えられる。一方、本発明の水素化精製触媒に含まれる有機化合物由来の炭素質物質は、特に担体上の固体酸性を有する活性点（酸点）の作用を阻害すると考えられる。酸点には、主として分解反応、あるいは分解反応と異性化反応の両方に対して活性をもつものと、主として水素化異性化に対して活性をもつものとが存在すると推定される。本実施形態の水素化精製触媒においては、炭素質物質が炭素原子換算で０．０５〜１質量％含まれることにより、この炭素質物質が選択的に、分解反応あるいは分解反応と異性化反応の両方に対して活性をもつ酸点に作用し、その活性を阻害するものと推定される。したがって、炭素質物質は一部水素化異性化活性を低下させるものの、その低下の幅は小さく、これに対して分解反応に対する活性を大幅に抑制することができると考えられる。その結果、必要なＣ１８異性体率を維持するために水素化異性化活性の低下が補われるように反応温度を高めても、分解反応が十分抑制されるために、従来の水素化精製触媒に比較して高い軽油留分収率を得ることができると推定される。 Although the mechanism of action in which the characteristics of the hydrorefining catalyst of this embodiment are manifested is not clear, the present inventors presume as follows. That is, the hydrorefining catalyst has two functions of hydrogenation-dehydrogenation ability with active metal and solid acidity possessed by the support. The hydroisomerization reaction and the hydrocracking reaction as a side reaction are considered to proceed by the two functions combined together. On the other hand, it is considered that the carbonaceous material derived from an organic compound contained in the hydrorefining catalyst of the present invention inhibits the action of active sites (acid sites) having solid acidity on the support. It is presumed that there are acid sites mainly having an activity with respect to a decomposition reaction or both of a decomposition reaction and an isomerization reaction, and those having an activity mainly with respect to a hydroisomerization. In the hydrotreating catalyst of the present embodiment, the carbonaceous material is selectively decomposed or decomposed and isomerized by containing 0.05 to 1% by mass in terms of carbon atoms. It is presumed that it acts on acid sites having activity against both and inhibits its activity. Therefore, although the carbonaceous material partially reduces the hydroisomerization activity, the range of the decrease is small, and it is considered that the activity for the decomposition reaction can be significantly suppressed. As a result, since the decomposition reaction is sufficiently suppressed even if the reaction temperature is increased so as to compensate for the decrease in hydroisomerization activity in order to maintain the necessary C 18 isomer ratio, the conventional hydrorefining catalyst It is estimated that a high gas oil fraction yield can be obtained compared to

中間留分水素化精製反応装置３２から排出される生成物は、気液分離器４２に導入され、液体生成物（液体炭化水素）と未反応の水素ガス及びガス状炭化水素を主成分とする気体成分とが分離される。液体炭化水素は下流の第２精留塔６０に導入され、気体成分は水素化処理反応に再利用される。   The product discharged from the middle distillate hydrotreating reactor 32 is introduced into the gas-liquid separator 42, and is mainly composed of a liquid product (liquid hydrocarbon), unreacted hydrogen gas and gaseous hydrocarbon. Gas components are separated. The liquid hydrocarbon is introduced into the second rectification column 60 downstream, and the gas component is reused for the hydrotreating reaction.

第１精留塔２０の塔頂から抜き出される粗ナフサは、ライン２を経て水素ガスと混合され、反応温度まで加熱されてナフサ留分水素化精製反応装置３０に供給され、水素化精製される。   The crude naphtha extracted from the top of the first rectifying column 20 is mixed with hydrogen gas via the line 2, heated to the reaction temperature, supplied to the naphtha fraction hydrotreating reactor 30, and hydrorefined. The

ナフサ留分水素化精製反応装置３０に充填される水素化精製触媒としては、公知の水素化精製触媒を用いることができるが、上述の本実施形態の水素化精製触媒を用いてもよい。ナフサ留分水素化精製反応装置３０においては、粗ナフサ留分に含まれるオレフィン類は水素化により飽和炭化水素に変換され、またアルコール類などの含酸素化合物は水素化脱酸素により炭化水素と水等とに変換される。なお、粗ナフサ留分は炭素数が概ね１０以下の炭化水素であり、その特性として、水素化異性化及び水素化分解は殆ど起こらない。   As the hydrotreating catalyst charged in the naphtha fraction hydrotreating reaction apparatus 30, a known hydrotreating catalyst can be used, but the above-described hydrotreating catalyst of the present embodiment may be used. In the naphtha fraction hydrotreating reactor 30, olefins contained in the crude naphtha fraction are converted into saturated hydrocarbons by hydrogenation, and oxygen-containing compounds such as alcohols are converted into hydrocarbons and water by hydrodeoxygenation. And so on. The crude naphtha fraction is a hydrocarbon having approximately 10 or less carbon atoms, and as a characteristic thereof, hydroisomerization and hydrocracking hardly occur.

粗ナフサ留分中にはオレフィン類及びアルコール類等の含酸素化合物が比較的に高い濃度で含まれ、これらを飽和炭化水素に転化する水素化精製反応においては、大きな反応熱が発生する。したがって、粗ナフサ留分のみを水素化精製に供すると、ナフサ留分水素化精製反応装置３０内でナフサ留分の温度が過度に上昇する場合がある。そこで、ナフサ留分水素化精製反応装置３０から排出される水素化精製されたナフサ留分の一部をライン１４によりナフサ留分水素化精製反応装置３０の上流のライン２にリサイクルすることにより、粗ナフサ留分を精製済みのナフサ留分により希釈して、水素化精製に供することが好ましい。   In the crude naphtha fraction, oxygen-containing compounds such as olefins and alcohols are contained at a relatively high concentration, and in the hydrorefining reaction for converting these into saturated hydrocarbons, a large heat of reaction is generated. Therefore, if only the crude naphtha fraction is subjected to hydrorefining, the temperature of the naphtha fraction may increase excessively in the naphtha fraction hydrotreating reactor 30. Therefore, by recycling a part of the hydrorefined naphtha fraction discharged from the naphtha fraction hydrotreating reactor 30 to the line 2 upstream of the naphtha fraction hydrotreating reactor 30 by the line 14, The crude naphtha fraction is preferably diluted with a purified naphtha fraction and subjected to hydrorefining.

ナフサ留分水素化精製反応装置３０における反応温度は、１８０〜４００℃、好ましくは２８０〜３５０℃、更に好ましくは３００〜３４０℃である。ここで、反応温度とは、ナフサ留分水素化精製反応装置３０内の触媒層の平均温度のことである。反応温度が前記下限温度以上であれば、粗ナフサ留分が充分に水素化精製され、前記上限温度以下であれば、触媒の寿命低下が抑制される。   The reaction temperature in the naphtha fraction hydrotreating reactor 30 is 180 to 400 ° C, preferably 280 to 350 ° C, more preferably 300 to 340 ° C. Here, the reaction temperature is the average temperature of the catalyst layer in the naphtha fraction hydrotreating reactor 30. When the reaction temperature is equal to or higher than the lower limit temperature, the crude naphtha fraction is sufficiently hydrorefined, and when the reaction temperature is equal to or lower than the upper limit temperature, a decrease in catalyst life is suppressed.

ナフサ留分水素化精製反応装置３０における圧力（水素分圧）は０．５〜１２ＭＰａであることが好ましく、１〜５ＭＰａであることがより好ましい。前記圧力が０．５ＭＰａ以上であれば、粗ナフサ留分が充分に水素化精製され、１２ＭＰａ以下であれば、設備の耐圧性を高めるための設備費を抑制できる。   The pressure (hydrogen partial pressure) in the naphtha fraction hydrotreating reactor 30 is preferably 0.5 to 12 MPa, and more preferably 1 to 5 MPa. If the pressure is 0.5 MPa or more, the crude naphtha fraction is sufficiently hydrorefined, and if it is 12 MPa or less, the equipment cost for increasing the pressure resistance of the equipment can be suppressed.

ナフサ留分水素化精製反応装置３０における液空間速度（ＬＨＳＶ［liquid hourly space velocity］）は０．１〜１０ｈ−１であることが好ましく、０．３〜３．５ｈ−１であることがより好ましい。ＬＨＳＶが０．１ｈ−１以上であれば、反応器の容積を過大にしなくてもよく、１０ｈ−１以下であれば、粗ナフサ留分が効率的に水素化精製される。 Liquid hourly space velocity in the naphtha fraction hydrotreating reactor 30 (LHSV [liquid hourly space velocity ]) is preferably from 0.1 to 10 -1, more to be 0.3 to 3.5 -1 preferable. If LHSV is 0.1 h −1 or more, the reactor volume does not need to be excessive, and if it is 10 h −1 or less, the crude naphtha fraction is efficiently hydrorefined.

ナフサ留分水素化精製反応装置３０における水素ガス／油比は５０〜１０００ＮＬ／Ｌであることが好ましく、７０〜８００ＮＬ／Ｌであることがより好ましい。ここで、「ＮＬ」とは、標準状態（０℃、１０１３２５Ｐａ）における水素容量（Ｌ）のことを意味する。水素ガス／油比が５０ＮＬ／Ｌ以上であれば、粗ナフサ留分が充分に水素化精製され、１０００ＮＬ／Ｌ以下であれば、多量の水素ガスを供給するための設備が不要となり、また運転コストの上昇を抑制できる。   The hydrogen gas / oil ratio in the naphtha fraction hydrotreating reactor 30 is preferably 50 to 1000 NL / L, and more preferably 70 to 800 NL / L. Here, “NL” means the hydrogen capacity (L) in the standard state (0 ° C., 101325 Pa). If the hydrogen gas / oil ratio is 50 NL / L or more, the crude naphtha fraction is sufficiently hydrorefined, and if it is 1000 NL / L or less, a facility for supplying a large amount of hydrogen gas is not required and the operation is continued. Increase in cost can be suppressed.

ナフサ留分水素化精製反応装置３０から排出された生成油は、気液分離器４０において未反応の水素ガスを主成分とする気体成分と、液体炭化水素とに気液分離される。気体成分は水素化処理反応に再利用され、液体炭化水素はライン５を経てナフサスタビライザー５０に供給され、Ｃ４以下のガス状炭化水素がライン８から除去され、主としてＣ５〜Ｃ１０からなるナフサ留分はライン９を経てナフサタンク７０に貯留される。 The product oil discharged from the naphtha fraction hydrotreating reactor 30 is gas-liquid separated in the gas-liquid separator 40 into a gaseous component mainly composed of unreacted hydrogen gas and liquid hydrocarbons. Gaseous components are recycled to the hydroprocessing reaction, the liquid hydrocarbons are supplied to the naphtha stabilizer 50 via a line 5, C 4 or less gaseous hydrocarbons are removed from the line 8, consisting mainly C 5 -C 10 The naphtha fraction is stored in the naphtha tank 70 via the line 9.

第１精留塔２０の塔底からライン４にて抜き出される粗ワックス留分は、ライン４に接続するライン１３によりリサイクルされる未分解ワックス（詳細は後述）及び水素ガスが混合され、反応温度まで加熱されてワックス留分水素化分解反応器３４に供給され、水素化分解される。   The crude wax fraction extracted from the bottom of the first rectifying column 20 at the line 4 is mixed with undecomposed wax (details will be described later) recycled by the line 13 connected to the line 4 and hydrogen gas. It is heated to a temperature and supplied to the wax fraction hydrocracking reactor 34 for hydrocracking.

ワックス留分水素化分解反応器３４に充填される水素化分解触媒としては、例えば、固体酸を含んで構成される担体に、活性金属として周期表第８〜１０族に属する金属を担持した触媒が挙げられる。   Examples of the hydrocracking catalyst charged in the wax fraction hydrocracking reactor 34 include a catalyst in which a metal belonging to Groups 8 to 10 of the periodic table is supported as an active metal on a carrier configured to contain a solid acid. Is mentioned.

好適な前記担体としては、超安定Ｙ（ＵＳＹ）型ゼオライト、Ｙ型ゼオライト、モルデナイトおよびβゼオライトなどの結晶性ゼオライト、ならびに、シリカアルミナ、シリカジルコニア、およびアルミナボリアなどの固体酸性を有する非晶性複合金属酸化物の中から選ばれる１種類以上の固体酸を含んで構成されるものが挙げられる。更に前記担体は、ＵＳＹ型ゼオライトと、シリカアルミナ、アルミナボリアおよびシリカジルコニアの中から選ばれる１種以上の固体酸とを含んで構成されるものがより好ましく、ＵＳＹ型ゼオライトと、アルミナボリア及び／又はシリカアルミナとを含んで構成されるものが更に好ましい。   Suitable carriers include crystalline zeolites such as ultra-stable Y (USY) zeolite, Y zeolite, mordenite and β zeolite, and amorphous having solid acidity such as silica alumina, silica zirconia, and alumina boria. The thing comprised including 1 or more types of solid acids chosen from composite metal oxides is mentioned. Further, the carrier is more preferably composed of USY zeolite and one or more solid acids selected from silica alumina, alumina boria and silica zirconia. USY zeolite, alumina boria and / or Or what is comprised including a silica alumina is still more preferable.

ＵＳＹ型ゼオライトの平均粒子径に特に制限はないが、好ましくは１．０μｍ以下、より好ましくは０．５μｍ以下である。また、ＵＳＹ型ゼオライトにおいて、シリカ／アルミナのモル比（アルミナに対するシリカのモル比）は１０〜２００であることが好ましく、１５〜１００であることがより好ましく、２０〜６０であることがさらに好ましい。   The average particle size of the USY zeolite is not particularly limited, but is preferably 1.0 μm or less, more preferably 0.5 μm or less. In the USY-type zeolite, the silica / alumina molar ratio (the molar ratio of silica to alumina) is preferably 10 to 200, more preferably 15 to 100, and still more preferably 20 to 60. .

また、前記担体は、結晶性ゼオライト０．１〜８０質量％と、固体酸性を有する非複合金属酸化物０．１〜６０質量％とを含んで構成されるものであることが好ましい。   Moreover, it is preferable that the said support | carrier is comprised including 0.1-80 mass% of crystalline zeolite and 0.1-60 mass% of non-complex metal oxides which have solid acidity.

前記担体は、上記固体酸とバインダとを含む担体組成物を成形した後、焼成することにより製造できる。固体酸の配合割合は、担体全体の質量を基準として１〜７０質量％であることが好ましく、２〜６０質量％であることがより好ましい。また、前記担体がＵＳＹ型ゼオライトを含んで構成される場合、ＵＳＹ型ゼオライトの配合割合は、担体全体の質量を基準として０．１〜１０質量％であることが好ましく、０．５〜５質量％であることがより好ましい。さらに、前記担体がＵＳＹ型ゼオライトおよびアルミナボリアを含んで構成される場合、ＵＳＹ型ゼオライトとアルミナボリアの配合比（ＵＳ型Ｙゼオライト／アルミナボリア）は、質量比で０．０３〜１であることが好ましい。また、前記担体がＵＳＹ型ゼオライトおよびシリカアルミナを含んで構成される場合、ＵＳＹ型ゼオライトとシリカアルミナとの配合比（ＵＳＹ型ゼオライト／シリカアルミナ）は、質量比で０．０３〜１であることが好ましい。   The carrier can be produced by molding a carrier composition containing the solid acid and a binder and then firing the carrier composition. The blending ratio of the solid acid is preferably 1 to 70% by mass, and more preferably 2 to 60% by mass based on the mass of the entire carrier. Moreover, when the said support | carrier is comprised including a USY type | mold zeolite, it is preferable that the mixture ratio of a USY type | mold zeolite is 0.1-10 mass% on the basis of the mass of the whole support | carrier, 0.5-5 mass % Is more preferable. Further, when the carrier is composed of USY zeolite and alumina boria, the blending ratio of USY zeolite to alumina boria (US type Y zeolite / alumina boria) is 0.03 to 1 by mass ratio. Is preferred. Moreover, when the said support | carrier is comprised including USY type | mold zeolite and silica alumina, the compounding ratio (USY type | mold zeolite / silica alumina) of USY type | mold zeolite and silica alumina is 0.03-1 in mass ratio. Is preferred.

バインダとしては、特に制限はないが、アルミナ、シリカ、チタニア、マグネシアが好ましく、アルミナがより好ましい。バインダの配合量は、担体全体の質量を基準として２０〜９８質量％であることが好ましく、３０〜９６質量％であることがより好ましい。   The binder is not particularly limited, but alumina, silica, titania and magnesia are preferable, and alumina is more preferable. The blending amount of the binder is preferably 20 to 98% by mass, and more preferably 30 to 96% by mass based on the mass of the entire carrier.

前記担体組成物の焼成温度は、４００〜５５０℃の範囲内にあることが好ましく、４７０〜５３０℃の範囲内であることがより好ましく、４９０〜５３０℃の範囲内であることがさらに好ましい。   The firing temperature of the carrier composition is preferably in the range of 400 to 550 ° C, more preferably in the range of 470 to 530 ° C, and even more preferably in the range of 490 to 530 ° C.

前記活性金属である周期表第８〜１０族の金属としては、具体的にはコバルト、ニッケル、ロジウム、パラジウム、イリジウム、白金などが挙げられる。これらのうち、ニッケル、パラジウムおよび白金、好ましくはパラジウムおよび白金の中から選ばれる金属を１種単独または２種以上組み合わせて用いることが好ましい。これらの金属は、含浸やイオン交換などの常法によって上述の担体に担持することができる。担持する金属量には特に制限はないが、当該金属がコバルト、ニッケル等の貴金属以外の金属である場合には、金属酸化物として担体の質量基準で２〜５０質量％程度であることが好ましい。また、当該金属が白金、パラジウム、ロジウム、イリジウム等の貴金属である場合には、金属の合計量が担体全体の質量に対して０．１〜３．０質量％であることが好ましい。水素化活性を有する金属の含有量が前記下限値未満の場合には、水素化分解が充分に進行しない傾向にある。一方、水素化活性を有する金属の含有量が前記上限値を超える場合には、水素化活性を有する金属の分散が低下して触媒の活性が低下する傾向となり、また触媒コストが上昇する。   Specific examples of metals in Groups 8 to 10 of the periodic table that are the active metals include cobalt, nickel, rhodium, palladium, iridium, and platinum. Among these, it is preferable to use one kind or a combination of two or more kinds of metals selected from nickel, palladium and platinum, preferably palladium and platinum. These metals can be supported on the above-mentioned carrier by a conventional method such as impregnation or ion exchange. The amount of metal to be supported is not particularly limited, but when the metal is a metal other than a noble metal such as cobalt or nickel, it is preferably about 2 to 50% by mass as a metal oxide based on the mass of the support. . Moreover, when the said metal is noble metals, such as platinum, palladium, rhodium, and iridium, it is preferable that the total amount of a metal is 0.1-3.0 mass% with respect to the mass of the whole support | carrier. When the content of the metal having hydrogenation activity is less than the lower limit, hydrogenolysis tends not to proceed sufficiently. On the other hand, when the content of the metal having hydrogenation activity exceeds the upper limit, the dispersion of the metal having hydrogenation activity tends to be reduced, and the activity of the catalyst tends to be reduced, and the catalyst cost is increased.

粗ワックス留分と未分解ワックスとの混合物（以下、「被処理ワックス」ということもある。）はワックス留分水素化分解反応装置３４において水素化分解されて、中間留分に相当する成分へと転換される。この際、粗ワックス留分に含まれるオレフィン類は水素化されてパラフィン炭化水素に転化され、アルコール類等の含酸素化合物は水素化脱酸素されてパラフィン炭化水素と水等とに転化される。また、同時に、燃料油基材としての低温流動性の向上に寄与するノルマルパラフィンの水素化異性化によるイソパラフィンの生成も進行する。また、被処理ワックスの一部は過度に水素化分解を受け、目的とする中間留分に相当する沸点範囲の炭化水素よりも更に低沸点のナフサ留分に相当する炭化水素に転換される。また、被処理ワックスの一部は水素化分解が更に進行し、ブタン類、プロパン、エタン、メタンなどの炭素数４以下のガス状炭化水素へと転換される。一方、被処理ワックスの一部は十分に水素化分解することなく未分解ワックスとしてワックス留分水素化分解反応装置３４から排出される。   A mixture of the crude wax fraction and the undecomposed wax (hereinafter also referred to as “wax to be treated”) is hydrocracked in the wax fraction hydrocracking reaction apparatus 34 to be a component corresponding to the middle fraction. Is converted. At this time, the olefins contained in the crude wax fraction are hydrogenated and converted into paraffin hydrocarbons, and oxygen-containing compounds such as alcohols are hydrodeoxygenated and converted into paraffin hydrocarbons and water. At the same time, the production of isoparaffin by hydroisomerization of normal paraffin that contributes to the improvement of low-temperature fluidity as a fuel oil base material also proceeds. Further, a part of the wax to be treated is excessively hydrocracked and converted to a hydrocarbon corresponding to a naphtha fraction having a lower boiling point than a hydrocarbon having a boiling range corresponding to the target middle distillate. In addition, a part of the wax to be treated undergoes hydrocracking, and is converted into gaseous hydrocarbons having 4 or less carbon atoms such as butanes, propane, ethane, and methane. On the other hand, part of the wax to be treated is discharged from the wax fraction hydrocracking reactor 34 as undecomposed wax without being sufficiently hydrocracked.

ワックス留分水素化分解反応装置３４における被処理ワックスの水素化分解においては、下記式（１）で定義される「分解率」を５０〜９０％、好ましくは６０〜８０％とすることが望ましい。
分解率（％）＝［（被処理ワックス単位質量中の沸点が３６０℃を超える炭化水素の質量）−（水素化分解生成物単位質量中の沸点が３６０℃を超える炭化水素の質量）］×１００／（被処理ワックス単位質量中の沸点が３６０℃を超える炭化水素の質量）…（１） In the hydrocracking of the wax to be treated in the wax fraction hydrocracking reactor 34, the “cracking rate” defined by the following formula (1) is 50 to 90%, preferably 60 to 80%. .
Decomposition rate (%) = [(mass of hydrocarbons whose boiling point in the treated wax unit mass exceeds 360 ° C.) − (Mass of hydrocarbons whose boiling point in the hydrocracking product unit mass exceeds 360 ° C.)] × 100 / (mass of hydrocarbons whose boiling point in the unit mass of wax to be treated exceeds 360 ° C.) (1)

前記分解率が５０％未満である場合には、被処理ワックスの水素化分解が不十分であり、水素化分解生成物中に占める中間留分に相当する沸点範囲の留分の比率が低下する。一方、分解率が９０％を超える場合には、被処理ワックスの分解が過度に進行し、中間留分の沸点範囲の下限を下回る沸点を有する炭化水素の生成が増加し、分解生成物中に占める中間留分の比率が低下する。分解率は、ワックス留分水素化分解反応装置３４における反応温度により制御する方法が一般的である。   When the cracking rate is less than 50%, the hydrocracking of the wax to be treated is insufficient, and the fraction of the boiling range corresponding to the middle fraction in the hydrocracking product decreases. . On the other hand, when the decomposition rate exceeds 90%, the decomposition of the wax to be treated proceeds excessively, the production of hydrocarbons having boiling points below the lower limit of the boiling range of the middle distillate increases, The proportion of middle distillates is reduced. Generally, the cracking rate is controlled by the reaction temperature in the wax fraction hydrocracking reactor 34.

なお、上記の「未分解ワックス」とは、被処理ワックスの中で、沸点が３６０℃以下となるまで水素化分解が進行しないものをいう。未分解ワックスは、後述する第２精留塔６０において塔底油として分離され、ワックス留分水素化分解反応装置３４にリサイクルされる。また、「水素化分解生成物」とは、特に断らない限り、ワックス留分水素化分解反応器３４から排出される未分解ワックスを含む全ての生成物を意味する。   The above “undecomposed wax” refers to a wax to be treated in which hydrocracking does not proceed until the boiling point becomes 360 ° C. or less. Undecomposed wax is separated as bottom oil in the second rectifying column 60 described later, and recycled to the wax fraction hydrocracking reactor 34. Further, the “hydrocracking product” means all products including the uncracked wax discharged from the wax fraction hydrocracking reactor 34 unless otherwise specified.

ワックス留分水素化分解反応器３４における反応温度（触媒床重量平均温度）としては、１８０〜４００℃が例示でき、好ましくは２００〜３７０℃、より好ましくは２５０〜３５０℃、さらに好ましくは２８０〜３５０℃である。反応温度が４００℃を超えると、水素化分解が過度に進行して、目的とする中間留分の収率が低下する傾向にある。また、水素化分解生成物が着色して、燃料基材としての使用が制限される場合もある。一方、反応温度が１８０℃より低い場合は、ワックス留分の水素化分解が十分に進行せず、中間留分の収率が低下する傾向にある。また、ワックス留分中のオレフィン類やアルコール類等の含酸素化合物が十分に除去されない傾向にある。   Examples of the reaction temperature (catalyst bed weight average temperature) in the wax fraction hydrocracking reactor 34 include 180 to 400 ° C, preferably 200 to 370 ° C, more preferably 250 to 350 ° C, and still more preferably 280 to 800 ° C. 350 ° C. When the reaction temperature exceeds 400 ° C., hydrocracking proceeds excessively, and the yield of the target middle distillate tends to decrease. In addition, the hydrocracking product may be colored to restrict use as a fuel base material. On the other hand, when the reaction temperature is lower than 180 ° C., the hydrocracking of the wax fraction does not proceed sufficiently, and the yield of the middle fraction tends to decrease. Further, oxygen-containing compounds such as olefins and alcohols in the wax fraction tend not to be sufficiently removed.

ワックス留分水素化分解反応器３４における水素分圧としては、例えば０．５〜１２ＭＰａであり、１．０〜５．０ＭＰａが好ましい。   The hydrogen partial pressure in the wax fraction hydrocracking reactor 34 is, for example, 0.5 to 12 MPa, and preferably 1.0 to 5.0 MPa.

ワックス留分水素化分解反応器３４における液空間速度（ＬＨＳＶ）としては、例えば０．１〜１０．０ｈ−１であり、０．３〜３．５ｈ−１が好ましい。水素ガスとワックス留分との比（水素ガス／油比）は、特に制限はないが、例えば５０〜１０００ＮＬ／Ｌであり、７０〜８００ＮＬ／Ｌが好ましい。ここで、「ＮＬ」とは、標準状態（０℃、１０１３２５Ｐａ）における水素容量（Ｌ）のことを意味する。水素ガス／油比が５０ＮＬ／Ｌ未満の場合には水素化分解が十分に進行しない傾向にあり、一方、１０００ＮＬ／Ｌを超える場合には、過大な水素供給源を必要とする傾向にある。 The liquid space velocity (LHSV) in the wax fraction hydrocracking reactor 34 is, for example, 0.1 to 10.0 h −1 , and preferably 0.3 to 3.5 h −1 . The ratio of the hydrogen gas to the wax fraction (hydrogen gas / oil ratio) is not particularly limited, but is, for example, 50 to 1000 NL / L, and preferably 70 to 800 NL / L. Here, “NL” means the hydrogen capacity (L) in the standard state (0 ° C., 101325 Pa). When the hydrogen gas / oil ratio is less than 50 NL / L, hydrocracking tends not to proceed sufficiently, while when it exceeds 1000 NL / L, an excessive hydrogen supply source tends to be required.

ワックス留分水素化分解反応装置３４から排出された水素化分解生成物は気液分離器４４において気液分離される。すなわち、未反応の水素ガス及び主としてＣ４以下の炭化水素ガスからなる気体成分と、ナフサ留分から未分解ワックスまでに相当する炭素数分布をもつ炭化水素油である液体成分とを分離する。分離された気体成分は水素化処理反応に再利用される。液体成分は、中間留分水素化精製反応装置３２から気液分離器４２を経て供給される中間留分の水素化精製物と混合され、第２精留塔６０へ供給される。 The hydrocracking product discharged from the wax fraction hydrocracking reactor 34 is gas-liquid separated in the gas-liquid separator 44. That is, a gas component composed of unreacted hydrogen gas and mainly hydrocarbon gas of C 4 or less is separated from a liquid component which is a hydrocarbon oil having a carbon number distribution corresponding to the naphtha fraction to the undecomposed wax. The separated gas component is reused for the hydrotreating reaction. The liquid component is mixed with the hydrolyzed product of the middle distillate supplied from the middle distillate hydrotreating reaction apparatus 32 via the gas-liquid separator 42 and supplied to the second rectifying column 60.

第２精留塔６０では、取り出す炭化水素油に応じてカット・ポイントを複数設定し、中間留分水素化精製反応装置３２から供給される中間留分の水素化精製物と、ワックス留分水素化分解反応装置３４から供給されるワックス留分の水素化分解物とからなる混合油の分留が行われる。   In the second rectifying column 60, a plurality of cut points are set according to the hydrocarbon oil to be extracted, and the hydrolysed product of the middle distillate supplied from the middle distillate hydrotreating reactor 32 and the wax distillate hydrogen are used. The mixed oil consisting of the hydrocracked product of the wax fraction supplied from the chemical cracking reactor 34 is fractionated.

本実施形態においてはカット・ポイントを１５０℃、２５０及び３６０℃に設定する。第２精留塔６０の塔頂からは、ライン１０によりナフサ留分を含む軽質留分が抜き出され、上述のナフサスタビライザー５０に供給され、Ｃ４以下の炭化水素ガスが除去されて、製品ナフサとしてナフサタンク７０に貯留される。第２精留塔６０の中央部からは、ライン１１により灯油留分が抜き出され、灯油タンク７２に貯留される。第２精留塔６０の下部からはライン１２により軽油留分が抜き出され、軽油タンク７４に貯留される。第２精留塔６０の塔底からはライン１３により未分解ワックスを主成分とする塔底油が抜き出され、ライン４にリサイクルされ、粗ワックス留分と共にワックス留分水素化分解反応装置３４に供給されて再度水素化分解される。 In the present embodiment, the cut points are set to 150 ° C., 250 and 360 ° C. From the top of the second rectifying column 60, a light fraction containing a naphtha fraction is extracted from the line 10 and supplied to the naphtha stabilizer 50 described above, and hydrocarbon gas of C 4 or less is removed. The naphtha is stored in the naphtha tank 70. A kerosene fraction is extracted from the center of the second rectifying tower 60 through the line 11 and stored in the kerosene tank 72. A light oil fraction is extracted from the lower part of the second rectifying column 60 through the line 12 and stored in the light oil tank 74. From the bottom of the second rectifying column 60, the bottom oil mainly composed of undecomposed wax is extracted by the line 13, recycled to the line 4, and the wax fraction hydrocracking reactor 34 together with the crude wax fraction. To be hydrocracked again.

以上のようにして、軽油留分、灯油留分、ナフサ留分が得られる。   As described above, a light oil fraction, a kerosene fraction, and a naphtha fraction are obtained.

本発明の炭化水素油の製造方法は上述の実施形態の例に限定されることはなく、本発明の趣旨を逸脱しない範囲において、種々の変更、追加等を行なうことができる。   The method for producing a hydrocarbon oil of the present invention is not limited to the above-described embodiment, and various modifications and additions can be made without departing from the spirit of the present invention.

例えば、上述の実施形態においては、ＦＴ合成反応装置から供給されるＦＴ合成油を、第１精留塔２０において粗ナフサ留分、粗中間留分及び粗ワックス留分に分留する形態としたが、この分留において、粗ナフサ留分と粗中間留分とを粗ナフサ・中間留分としてひとつの留分として分留してもよい。そして、前記粗ナフサ・中間留分を、本発明の水素化精製触媒が充填された単一の水素化精製反応装置において水素化精製に供してもよい。   For example, in the above-described embodiment, the FT synthetic oil supplied from the FT synthesis reaction apparatus is fractionated into a crude naphtha fraction, a crude middle fraction, and a crude wax fraction in the first rectifying column 20. However, in this fractionation, the crude naphtha fraction and the crude middle distillate may be fractionated as one fraction as a crude naphtha / middle fraction. The crude naphtha / middle distillate may be subjected to hydrorefining in a single hydrorefining reaction apparatus packed with the hydrorefining catalyst of the present invention.

更には、ＦＴ合成油を第１精留塔２０において分留することなく、ＦＴ合成反応装置内の温度において気液分離することにより、当該温度において気体となる軽質炭化水素を冷却して液化させた軽質液体炭化水素と、当該温度において液体である重質液体炭化水素とに分別してもよい。そして、ナフサ留分水素化精製反応装置３０を設けることなく、前記軽質液体炭化水素を、本発明の水素化精製触媒が充填された中間留分水素化精製反応装置３２において水素化精製に供し、前記重質液体炭化水素を、ワックス留分水素化分解反応装置３４において水素化分解に供してもよい。   Furthermore, by separating the FT synthetic oil at the temperature in the FT synthesis reactor without fractionating it in the first rectification column 20, the light hydrocarbons that become gas at the temperature are cooled and liquefied. The light liquid hydrocarbon may be separated from the heavy liquid hydrocarbon that is liquid at the temperature. Then, without providing the naphtha fraction hydrotreating reactor 30, the light liquid hydrocarbon is subjected to hydrorefining in the middle fraction hydrotreating reactor 32 packed with the hydrotreating catalyst of the present invention, The heavy liquid hydrocarbon may be subjected to hydrocracking in the wax fraction hydrocracking reactor 34.

また、上述の実施形態においては、中間留分水素化精製反応装置３２から排出される水素化精製された中間留分と、ワックス留分水素化分解反応装置３４から排出されるワックス留分の水素化分解生成物との混合物を第２精留塔６０にて分留する形態としたが、これに限定されることはなく、例えば中間留分水素化精製反応装置３２から排出される水素化精製された中間留分と、ワックス留分水素化分解反応装置３４から排出されるワックス留分の水素化分解生成物とを、それぞれ別の精留塔において分留してもよい。   Further, in the above-described embodiment, the hydrogen-purified middle fraction discharged from the middle fraction hydrotreating reaction apparatus 32 and the hydrogen of the wax fraction discharged from the wax fraction hydrocracking reaction apparatus 34 are used. Although the mixture with the pyrolysis product is fractionated in the second rectification column 60, the present invention is not limited to this. For example, hydrorefining discharged from the middle distillate hydrotreating reactor 32. The intermediate fraction and the hydrocracked product of the wax fraction discharged from the wax fraction hydrocracking reaction apparatus 34 may be fractionated in separate rectification columns.

更に、上述の実施形態においては、製品としてナフサ留分、灯油留分、軽油留分を得たが、灯油留分及び軽油留分をひとつの留分（中間留分）として回収してもよい。   Furthermore, in the above-described embodiment, a naphtha fraction, a kerosene fraction, and a gas oil fraction were obtained as products, but the kerosene fraction and the gas oil fraction may be recovered as one fraction (intermediate fraction). .

以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

（実施例１）
＜水素化精製触媒の調製＞
粉末状のシリカジルコニア（シリカ単位／ジルコニア単位モル比が７）を６０質量％と粉末状のアルミナを４０質量％とを含有する組成物に水を加えて粘土状に混練し、ここに成型助剤としてデンプンを、シリカジルコニアとアルミナとの合計の質量に対して５質量％の割合で配合し、更に混練を行なって捏和物を調製した。この捏和物を押出成型により直径約１．５ｍｍ、長さ約３ｍｍの円柱状に成型した。得られた成型体を１２０℃で３時間乾燥し、更に空気中、４５０℃で３時間焼成して担体を得た。この担体中に含まれるデンプン由来の炭素原子を含む残留物の含有量を、堀場製作所社製炭素・硫黄分析装置ＥＭＩＡ−９２０Ｖを用いて測定した結果、担体の質量を基準として１．１質量％であった。 Example 1
<Preparation of hydrotreating catalyst>
Water is added to a composition containing 60% by mass of powdered silica zirconia (silica unit / zirconia unit molar ratio: 7) and 40% by mass of powdered alumina, and the mixture is kneaded into a clay and molded into this composition. Starch was blended at a ratio of 5% by mass with respect to the total mass of silica zirconia and alumina, and kneaded to prepare a kneaded product. This kneaded product was molded into a cylindrical shape having a diameter of about 1.5 mm and a length of about 3 mm by extrusion molding. The obtained molded body was dried at 120 ° C. for 3 hours and further calcined in air at 450 ° C. for 3 hours to obtain a carrier. The content of the residue containing carbon atoms derived from starch contained in this carrier was measured using a carbon / sulfur analyzer EMIA-920V manufactured by Horiba, Ltd. As a result, 1.1% by mass based on the mass of the carrier. Met.

この担体を、担体の質量を基準とし、白金原子として０．８質量％となる量のジクロロテトラアンミン白金（ＩＩ）の水溶液により、Ｉｎｃｉｐｉｅｎｔ ｗｅｔｎｅｓｓ法を用いて含浸し、更にこれを１２０℃で３時間乾燥して触媒前駆体を得た。   The carrier was impregnated with an aqueous solution of dichlorotetraammineplatinum (II) in an amount of 0.8% by mass as platinum atoms based on the mass of the carrier, using the Incipient wetness method, and this was further impregnated at 120 ° C. for 3 hours. The catalyst precursor was obtained by drying.

次に上記で得られた触媒前駆体を焼成した。加熱炉内に触媒前駆体を仕込み、空気雰囲気下で、３００℃まで昇温し、その後３００〜４００℃の間を１０℃／ｈの昇温速度で昇温し、その後５００℃にて１時間焼成することにより、水素化精製触媒を得た。得られた水素化精製触媒中の炭素質物質を前述の炭素・硫黄分析装置により定量した結果、触媒の質量を基準とし、炭素原子換算で０．０６質量％であった。   Next, the catalyst precursor obtained above was calcined. A catalyst precursor is charged into a heating furnace, heated to 300 ° C. in an air atmosphere, and then heated at a rate of 10 ° C./h between 300 and 400 ° C., and then at 500 ° C. for 1 hour. By calcination, a hydrorefining catalyst was obtained. As a result of quantifying the carbonaceous material in the obtained hydrorefining catalyst with the above-mentioned carbon / sulfur analyzer, it was 0.06% by mass in terms of carbon atom based on the mass of the catalyst.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を固定床流通式反応器に充填し、水素気流下、３４０℃で４時間の還元処理を行って触媒を活性化した。 <Manufacture of hydrocarbon oil>
The hydrorefining catalyst obtained as described above was charged into a fixed bed flow reactor, and the catalyst was activated by performing a reduction treatment at 340 ° C. for 4 hours under a hydrogen stream.

次に、ＦＴ合成反応により得られたＦＴ合成油を精留塔により分留し、沸点が１５０〜３６０℃の範囲にある中間留分の炭化水素油（Ｃ１１〜Ｃ２１）を原料油として得た。この原料油を分析した結果、３．６質量％のオレフィン分及び４．０質量％の含酸素化合物を含むノルマルパラフィンであった。 Next, the FT synthetic oil obtained by the FT synthesis reaction is fractionated by a rectifying column, and the middle-distilled hydrocarbon oil (C 11 to C 21 ) having a boiling point in the range of 150 to 360 ° C. is used as a raw material oil. Obtained. As a result of analyzing this raw material oil, it was a normal paraffin containing 3.6% by mass of an olefin and 4.0% by mass of an oxygen-containing compound.

上記原料油を、前記水素化精製触媒を充填した固定床流通式反応器に、水素ガスと共に供給して水素化精製（水素化精製反応及び水素化異性化反応）を行なった。反応条件は、反応圧力（水素ガスの圧力）を３．０ＭＰａ、ＬＨＳＶを２．０ｈ−１、水素／油比を３４０ＮＬ／Ｌとした。また、生成物中のオクタデカン（Ｃ１８）についてガスクロマトグラフィー法により分析を行い、全オクタデカンに対する分枝鎖を有するオクタデカン（イソオクタデカン）の比率（１００×イソオクタデカンの質量／全オクタデカンの質量、Ｃ１８異性体率）を算出し、このＣ１８異性体率が８５％となるように反応温度を決定した。反応温度は３３６℃であった。 The raw material oil was supplied together with hydrogen gas to a fixed bed flow reactor filled with the hydrorefining catalyst to perform hydrorefining (hydrorefining reaction and hydroisomerization reaction). The reaction conditions were such that the reaction pressure (hydrogen gas pressure) was 3.0 MPa, LHSV was 2.0 h −1 , and the hydrogen / oil ratio was 340 NL / L. Further, octadecane (C 18 ) in the product is analyzed by gas chromatography, and the ratio of octadecane having a branched chain to all octadecane (isooctadecane) (100 × mass of isooctadecane / mass of all octadecane, C 18 isomer ratio) was calculated, and the reaction temperature was determined so that the C 18 isomer ratio was 85%. The reaction temperature was 336 ° C.

反応器から排出された生成物を熱交換器により約３５℃に冷却し、気液分離器によりガス成分と液体成分を分離し、液体成分（炭化水素油）を精留塔に供給し、２５０℃をカットポイントとして分留を行い、沸点２５０℃以上の留分を軽油留分として回収した。そして、供給した原料油の質量流量に対する精留塔からの軽油留分の抜き出し流量の比率から、軽油留分の収率を算出した。軽油留分の収率は４３質量％であった。なお、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表１に示す。   The product discharged from the reactor is cooled to about 35 ° C. by a heat exchanger, a gas component and a liquid component are separated by a gas-liquid separator, and a liquid component (hydrocarbon oil) is supplied to a rectifying column. Fractionation was carried out at a cut point of ℃, and a fraction having a boiling point of 250 ℃ or higher was recovered as a light oil fraction. And the yield of the light oil fraction was computed from the ratio of the extraction flow rate of the light oil fraction from the fractionator with respect to the mass flow rate of the supplied raw material oil. The yield of the light oil fraction was 43% by mass. The liquid hydrocarbon separated by the gas-liquid separator did not substantially contain an olefin component and an oxygen-containing compound. The results are shown in Table 1.

（実施例２）
＜水素化精製触媒の調製＞
触媒前駆体の焼成において、５００℃における焼成時間を０．５時間とした以外は実施例１と同様の方法にて水素化精製触媒を得た。水素化精製触媒中の炭素質物質の含有量は炭素原子換算で０．３質量％であった。 (Example 2)
<Preparation of hydrotreating catalyst>
In the calcination of the catalyst precursor, a hydrorefining catalyst was obtained in the same manner as in Example 1 except that the calcination time at 500 ° C. was 0.5 hour. The content of the carbonaceous substance in the hydrotreating catalyst was 0.3% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３３８℃であり、軽油留分の収率は４４質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表１に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 338 ° C., and the yield of the gas oil fraction was 44% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 1.

（実施例３）
＜水素化精製触媒の調製＞
実施例１と同様にして触媒前駆体を調製した。この触媒前駆体を加熱炉内に仕込み、３００℃まで昇温し、その後３００〜４００℃の間を１０℃／ｈの昇温速度で昇温し、その後４８０℃にて０．５時間焼成することにより、水素化精製触媒を得た。水素化精製触媒中の炭素質物質の含有量は炭素原子換算で０．８質量％であった。 (Example 3)
<Preparation of hydrotreating catalyst>
A catalyst precursor was prepared in the same manner as in Example 1. This catalyst precursor is charged into a heating furnace, heated to 300 ° C., then heated between 300 and 400 ° C. at a heating rate of 10 ° C./h, and then calcined at 480 ° C. for 0.5 hour. As a result, a hydrorefining catalyst was obtained. The content of the carbonaceous substance in the hydrotreating catalyst was 0.8% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３３９℃であり、軽油留分の収率は４４質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表１に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 339 ° C., and the yield of the gas oil fraction was 44% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 1.

（実施例４）
＜水素化精製触媒の調製＞
実施例１と同様にして、シリカジルコニアとアルミナと水とデンプンから捏和物を調製し、この捏和物を成型し、これを乾燥して成型体を得た。この成型体を空気中、５５０℃で３時間焼成して担体を得た。この担体中に含まれるデンプン由来の炭素原子を含む残留物の含有量を実施例１と同様に測定したところ、炭素原子は検出されなかった（炭素原子換算の含有量が０．０２質量％以下）。 Example 4
<Preparation of hydrotreating catalyst>
In the same manner as in Example 1, a kneaded product was prepared from silica zirconia, alumina, water, and starch, the kneaded product was molded, and dried to obtain a molded body. This molded body was calcined in air at 550 ° C. for 3 hours to obtain a carrier. When the content of the residue containing the carbon atom derived from starch contained in the carrier was measured in the same manner as in Example 1, no carbon atom was detected (the content in terms of carbon atom was 0.02% by mass or less). ).

このようにして得た担体に、実施例１と同様にしてジクロロテトラアンミン白金（ＩＩ）を担持し、乾燥して触媒前駆体を得た。この触媒前駆体を５００℃にて１時間焼成し、一旦触媒（「予備触媒」という。）を得た。   The carrier thus obtained was loaded with dichlorotetraammineplatinum (II) in the same manner as in Example 1 and dried to obtain a catalyst precursor. This catalyst precursor was calcined at 500 ° C. for 1 hour to obtain a catalyst (referred to as “preliminary catalyst”).

次に、この予備触媒を、実施例１においてＦＴ合成油を分留して得た中間留分を水素化精製して得た軽油留分に浸漬した。そして、予備触媒を軽油留分から取り出し、窒素気流中で３００℃にて３時間脱油処理を行なった。   Next, this preliminary catalyst was immersed in a light oil fraction obtained by hydrorefining the middle fraction obtained by fractionating FT synthetic oil in Example 1. Then, the preliminary catalyst was taken out from the light oil fraction, and deoiled for 3 hours at 300 ° C. in a nitrogen stream.

次に、脱油処理後の予備触媒を加熱炉内に仕込み、空気雰囲気下で、３００℃まで昇温し、その後３００〜４００℃の間を１０℃／ｈの昇温速度で昇温し、その後４５０℃にて２時間焼成することにより、水素化精製触媒を得た。この水素化精製触媒中の炭素質物質の含有量は炭素原子換算で０．０８質量％であった。   Next, the pre-catalyst after the deoiling treatment is charged into a heating furnace, heated to 300 ° C. in an air atmosphere, and then heated between 300 and 400 ° C. at a heating rate of 10 ° C./h. Thereafter, it was calcined at 450 ° C. for 2 hours to obtain a hydrorefining catalyst. The content of the carbonaceous substance in the hydrorefining catalyst was 0.08% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３３７℃であり、軽油留分の収率は４４質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表２に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 337 ° C., and the yield of the gas oil fraction was 44% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 2.

（実施例５）
＜水素化精製触媒の調製＞
軽油留分に浸漬し、脱油処理を行った予備触媒の焼成において、４５０℃での焼成時間を０．８時間とした以外は実施例４と同様にして水素化精製触媒を得た。この水素化精製触媒中の炭素質物質の含有量は炭素原子換算で０．４質量％であった。 (Example 5)
<Preparation of hydrotreating catalyst>
A hydrorefining catalyst was obtained in the same manner as in Example 4 except that, in the calcining of the pre-catalyst immersed in the light oil fraction and subjected to the deoiling treatment, the calcining time at 450 ° C. was changed to 0.8 hours. The content of the carbonaceous substance in this hydrotreating catalyst was 0.4% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３３９℃であり、軽油留分の収率は４５質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表２に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 339 ° C., and the yield of the gas oil fraction was 45% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 2.

（比較例１）
＜水素化精製触媒の調製＞
実施例１と同様にして触媒前駆体を調製した。この触媒前駆体を加熱炉内に仕込み、空気雰囲気下で、３００℃まで昇温し、その後３００〜４００℃の間を１０℃／ｈの昇温速度で昇温し、その後６００℃にて０．５時間焼成することにより、水素化精製触媒を得た。この水素化精製触媒中の炭素質物質の含有量は炭素原子換算で０．０３質量％であった。 (Comparative Example 1)
<Preparation of hydrotreating catalyst>
A catalyst precursor was prepared in the same manner as in Example 1. The catalyst precursor was charged into a heating furnace, heated to 300 ° C. in an air atmosphere, then heated to 300 to 400 ° C. at a heating rate of 10 ° C./h, and then 0 ° C. at 600 ° C. The hydrorefining catalyst was obtained by baking for .5 hours. The content of the carbonaceous material in this hydrotreating catalyst was 0.03% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３３４℃であり、軽油留分の収率は４１質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表１に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 334 ° C., and the yield of the gas oil fraction was 41% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 1.

（比較例２）
＜水素化精製触媒の調製＞
軽油留分に浸漬し、脱油処理を行った予備触媒の焼成を、昇温後４７０℃、２時間にて行なった以外は実施例４と同様の操作にて水素化精製触媒を得た。この水素化精製触媒中の炭素質物質の含有量は炭素原子換算で０．０３質量％であった。 (Comparative Example 2)
<Preparation of hydrotreating catalyst>
A hydrorefining catalyst was obtained in the same manner as in Example 4 except that the pre-catalyst immersed in the light oil fraction and subjected to the deoiling treatment was calcined at 470 ° C. for 2 hours after the temperature rise. The content of the carbonaceous material in this hydrotreating catalyst was 0.03% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３３４℃であり、軽油留分の収率は４１質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表２に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 334 ° C., and the yield of the gas oil fraction was 41% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 2.

（比較例３）
＜水素化精製触媒の調製＞
軽油留分に浸漬し、脱油処理を行った予備触媒の焼成を、昇温後４５０℃、０．５時間にて行なった以外は実施例４と同様の操作にて水素化精製触媒を得た。この水素化精製触媒中の炭素質物質の含有量は炭素原子換算で１．５質量％であった。 (Comparative Example 3)
<Preparation of hydrotreating catalyst>
A hydrorefining catalyst was obtained in the same manner as in Example 4 except that the pre-catalyst immersed in the light oil fraction and subjected to deoiling was calcined at 450 ° C. for 0.5 hour after the temperature was raised. It was. The content of the carbonaceous substance in the hydrorefining catalyst was 1.5% by mass in terms of carbon atoms.

＜炭化水素油の製造＞
上記により得られた水素化精製触媒を用いて、実施例１と同様にしてＦＴ合成油由来の中間留分の水素化精製を行なった。Ｃ１８異性体率が８５％となる反応温度は３４１℃であり、軽油留分の収率は４３質量％であった。また、前記気液分離器により分離された液体炭化水素中には、オレフィン分及び含酸素化合物は実質的に含まれていなかった。結果を表２に示す。 <Manufacture of hydrocarbon oil>
Using the hydrorefining catalyst obtained above, the middle distillate derived from FT synthetic oil was hydrorefined in the same manner as in Example 1. The reaction temperature at which the C 18 isomer ratio was 85% was 341 ° C., and the yield of the gas oil fraction was 43% by mass. Further, the liquid hydrocarbons separated by the gas-liquid separator were substantially free of olefin and oxygen-containing compounds. The results are shown in Table 2.

Figure 0005690634
Figure 0005690634

Figure 0005690634
Figure 0005690634

表１及び表２の結果から、炭素質物質の含有量が０．０５〜１質量％である実施例の水素化精製触媒によれば、炭素質物質の含有量が０．０５質量％未満である水素化精製触媒に比較して、同一のＣ１８異性体率において、高い軽油留分収率が得られることが明らかとなった。また、炭素質物質の含有量が１質量％を超える水素化精製触媒にあっては、同一のＣ１８異性体率において、比較的高い軽油収率を得ることはできるが、同一のＣ１８異性体率を得るための反応温度が高くなり、触媒の寿命の点で問題となる。 From the results of Table 1 and Table 2, according to the hydrorefining catalyst of the example in which the content of the carbonaceous material is 0.05 to 1% by mass, the content of the carbonaceous material is less than 0.05% by mass. It has been found that high gas oil fraction yields can be obtained at the same C18 isomer ratio compared to certain hydrorefining catalysts. In addition, in the hydrorefining catalyst having a carbonaceous substance content exceeding 1% by mass, a relatively high gas oil yield can be obtained at the same C18 isomer ratio, but the same C18 isomerism can be obtained. The reaction temperature for obtaining the volume fraction becomes high, which causes a problem in terms of the life of the catalyst.

２０…第１精留塔、３０…ナフサ留分水素化精製反応装置、３２…中間留分水素化精製反応器、３４…ワックス留分水素化分解反応器、５０…第２精留塔、１００…炭化水素油の製造装置。   DESCRIPTION OF SYMBOLS 20 ... 1st fractionator, 30 ... Naphtha fraction hydrorefining reactor, 32 ... Middle fraction hydrorefining reactor, 34 ... Wax fraction hydrocracking reactor, 50 ... 2nd fractionator, 100 ... Hydrocarbon oil production equipment.

Claims (4)

固体酸性を有する非晶性複合金属酸化物を含む担体と、前記担体に担持された周期表第８族〜第１０族の貴金属から選択される少なくとも一種の活性金属と、を含有してなる水素化精製触媒であって、
前記水素化精製触媒は、炭素原子を含む炭素質物質を含有し、
前記水素化精製触媒における前記炭素質物質の含有量が炭素原子換算で０．０５〜１質量％である、フィッシャー・トロプシュ合成反応により得られる合成油を水素化精製するために用いられる、水素化精製触媒。 Hydrogen containing a support containing an amorphous composite metal oxide having solid acidity and at least one active metal selected from Group 8 to Group 10 noble metals supported on the support Purification catalyst,
The hydrorefining catalyst contains a carbonaceous material containing carbon atoms,
Hydrogenation used for hydrorefining synthetic oil obtained by Fischer-Tropsch synthesis reaction, wherein the content of the carbonaceous material in the hydrorefining catalyst is 0.05 to 1% by mass in terms of carbon atoms Purification catalyst. 前記非晶性複合金属酸化物が、シリカジルコニア、シリカアルミナ及びアルミナボリアから選択される少なくとも一種である、請求項１記載の水素化精製触媒。   The hydrorefining catalyst according to claim 1, wherein the amorphous composite metal oxide is at least one selected from silica zirconia, silica alumina, and alumina boria. 前記活性金属が白金である、請求項１又は２記載の水素化精製触媒。   The hydrorefining catalyst according to claim 1 or 2, wherein the active metal is platinum. 分子状水素の共存下、沸点が２５〜３６０℃の範囲にある直鎖状脂肪族炭化水素を８０質量％以上含み且つ沸点が１５０〜３６０℃の範囲にある直鎖状脂肪族炭化水素を２０質量％以上含む原料油を、請求項１〜３のいずれか一項記載の水素化精製触媒に接触させる工程を有し、
前記原料油が、フィッシャー・トロプシュ合成反応により得られる合成油である、炭化水素油の製造方法。
In the presence of molecular hydrogen, 20 linear aliphatic hydrocarbons containing 80 mass% or more of linear aliphatic hydrocarbons having a boiling point in the range of 25 to 360 ° C. and having boiling points in the range of 150 to 360 ° C. are 20 Having a step of bringing a raw material oil containing at least mass% into contact with the hydrorefining catalyst according to any one of claims 1 to 3,
A method for producing a hydrocarbon oil, wherein the raw material oil is a synthetic oil obtained by a Fischer-Tropsch synthesis reaction.
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